cover q109 9/12/08 12:22 Page 1

ptq
Q1 2009
ptq
Q1 2009

PETROLEUM TECHNOLOGY QUARTERLY

REFINING
GAS PROCESSING
PETROCHEMICALS
OUTLOOK 2009
AUTOMATION AND CONTROL
ENVIRONMENTAL

SPECIAL FEATURES
OUTLOOK 2009
AUTOMATION AND CONTROL
ENVIRONMENTAL
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ptq
PETROLEUM TECHNOLOGY QUARTERLY
5 Waiting for profitability
René G Gonzalez

7 Outlook 2009
Q1 (Jan, Feb, Mar) 2009 19 Processing Trends
www.eptq.com
23 ptq&a
25 FCC reactor design: part II
Warren Letzsch, Chris Santner and Steve Tragesser The Shaw Group

31 Stabilisation of asphaltenes
Berthold Otzisk and Hermann Kempen Kurita Europe

39 Maximising diesel recovery from crude

Scott W Golden Process Consulting Services

47 Online cleaning improves operational excellence

Marcello Ferrara ITW

55 Increasing FCC yields with oxygen enrichment

Jack Olesen Praxair

59 New roles for FCCU: carbon capture unit and coke gasifier
Erich J Mace, Adrienne M Blume and Thomas W Yeung
Hydrocarbon Publishing Company

65 Oil sands industry status

Tony Pavone SRI Consulting

77 Beyond turnaround planning

Brian Cormier Resource Development Company
Charles F Gillard C F Gillard and Associates

83 Improving VGO hydrotreater operation

Darius Remesat Koch-Glitsch Canada

91 Clean diesel hydrotreating

Ed Palmer, Stan Polcar and Anne Wong Mustang Engineering

103 Pygas upgrading for European steam crackers

Joseph C Gentryn and Meijuan Zeng GTC Technology

111 Control of primary fractionator fouling

Bob Presenti, Dan Frye and Sandra Linares-Samaniego Nalco Company

117 Reducing FCC regenerator emissions

Chris Kuehler, Pieter van de Gender and Subramani Ramachandran
Albemarle Corporation

127 SO2 scrubbing in refinery applications

Rick W Birnbaum Cansolv Technologies

137 Industry News

142 New Products

The hydrocracker unit of Ruhr Oel, located in Gelsenkirchen, Germany.

Photo courtesy of Ruhr Oel

©2009. The entire content of this publication is protected by copyright full details of which are available from the publishers. All
rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any
means – electronic, mechanical, photocopying, recording or otherwise – without the prior permission of the copyright owner.
The opinions and views expressed by the authors in this publication are not necessarily those of the editor or publisher and while
every care has been taken in the preparation of all material included in Petroleum Technology Quarterly the publisher cannot be held
responsible for any statements, opinions or views or for any inaccuracies.
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 ptqPETROLEUM TECHNOLOGY QUARTERLY

Vol 14 No 1
Waiting for
profitability
Q1 (Jan, Feb, Mar) 2009

B
Editor y now, the industry has had some time to consider what to do about the low
René G Gonzalez demand and oversupply of a range of refinery and petrochemical products.
editor@petroleumtechnology.com
As discussed by the executives who participated in Outlook 2009, instability
in feedstock pricing since last summer has made it difficult for downstream
Production Editor managers to make their business models work. It is no secret that the industry has
Rachel Zamorski entered a down cycle after a solid four years of strong growth. Going forward, high
production@petroleumtechnology.com complexity processors will be better positioned to ride this cycle.
Although crude prices were dipping to $50/bbl at the time of going to press, prices
are expected to increase, but not above $100/bbl any time soon. More importantly,
Graphics Editor a stable pricing environment will create stable margins for the refining sector. While
Mohammed Samiuddin the sweet spot going into 2009 will probably be $60–80 per barrel, or even $60–100,
graphics@petroleumtechnology.com
many refiners will be able to make their business models work in this scenario. It is
when energy goes in a straight line from $80–140, or back down again from $140–
Editorial 80, that it becomes difficult for managers to plan and projects get put on hold or
PO Box 11283 cancelled, which is what has been happening since last year.
Spring TX 77391, USA Interestingly, the sharp decline in crude oil prices has not greatly affected some
tel +1 281 374 8240 technology licensors and E&C contractors to date. For example, the backlog of
fax +1 281 257 0582 business at Fluor is because their clients have long-term expectations of a higher
price for oil instead of today’s depressed price. Outside of other industries, such as
nuclear, Fluor derives half of its business from both upstream and downstream oil
Advertising Sales Manager and gas services. According to Fluor CEO Alan Boeckmann, these capital projects are
Paul Mason
based on long-term assumptions for crude to realise an average of $50 or even $60
sales@petroleumtechnology.com
per barrel. There are areas where technology, engineering and equipment suppliers
will remain busy as the industry rides through the current down cycle, such as with
Advertising Sales increasing refinery distillate production, efficiency improvements and the major
Bob Aldridge regulatory initiatives shaping the refining and petrochemical industry.
sales@petroleumtechnology.com In the past, the petrochemical cycle, from peak-to-peak, ran for around seven to
nine years, but this time the cycle had expanded to 11–12 years due to steadily rising
crude oil prices up until Q3 2008 and strong Asian economies, especially China and
Advertising Sales Office India. China, now the world’s largest petrochemical importer, began importing
tel +44 870 90 303 90
significant quantities of basic petrochemicals after 2004, so much so that, like other
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products such as cement and steel, this resulted in significant increases in global
Publisher petrochemical prices. However, the petrochemical cycle began its downward cycle
Nic Allen earlier than expected due to the financial crisis and impending worldwide economic
publisher@petroleumtechnology.com slow-down. Meanwhile, new petrochemical production capacity will be the key item
pressuring petrochemical prices. Whether or not these prices will drop as much as
Circulation in past downturns is difficult to predict and seems to depend on which expert you
Jacki Watts talk to.
circulation@petroleumtechnology.com To be sure, this oversupply and drop in petrochemical prices will be leveraged by
the cost-advantaged ethane-based steam crackers in the Middle East to support high
Crambeth Allen Publishing Ltd
operating rates, while producers in other regions will be forced to cut back
Hopesay, Craven Arms SY7 8HD, UK
tel +44 870 90 600 20 production. This has already been happening, with certain naphtha-based steam
fax +44 870 90 600 40 crackers in Europe and the US Gulf Coast shutting down or scaling back since last
November. The cost of ethylene production back in 2007 reached well over
ISSN 1362-363X $700 per tonne in Western Europe and the US (mainly due to the cost of naphtha
feedstocks), while the cost for a typical gas-based producer in the Middle East
remained under $100 per tonne. To compound this challenge for naphtha-based
Petroleum Technology Quarterly (USPS crackers, propylene demand, increasing by as much as 5.5% per year, has begun
0014-781) is published quarterly plus decreasing to 4.5% or less since October 2008. Along with the capacity developments
annual Catalysis edition by Crambeth Allen
Publishing Ltd and is distributed in the USA in the Middle East is acceleration in Asian capacity, primarily in China. Chinese
by SPP, 75 Aberdeen Rd, Emigsville, PA 17318. cracker projects, developed in joint ventures with global downstream organisations
Periodicals postage paid at Emigsville PA.
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such as BASF, Shell and BP, are highly integrated with refineries and exploit the
Petroleum Technology Quarterly c/o PO advantages of lower fixed costs and proximity to market, relative to investments in
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the Middle East.
at $25 per copy inc postage. In summary, high complexity, lower fixed costs and market proximity will be key
to riding out this down cycle. However, it is too early to tell when we will see the
trough in this cycle. At the end of the day, it is up to the consumer.

René G Gonzalez

PTQ Q1 2009 5
 Travel with us,
and you’re always
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 Outlook for 2009
What are the important trends and issues affecting the downstream processing industry
this new year? Executives and industry experts in the following pages forecast industry
challenges and prospects that could affect profitability

Gene Davio developed with rigour by the EPC contractor who will
implement them.
Senior Vice President, Definitely, the market has changed dramatically. While
Downstream Operations the future is never certain, the project teams that work now
Fluor Corporation to position themselves to react to the opportunities that have
been created by these changing conditions will have the
greatest level of success.

T
he recent economic crisis
has resulted in an outlook
for 2009 that is rapidly
changing and difficult to predict. Guillermo Guariguata U
While the current climate is President
causing many owners to consider
the viability and timing of new Onyx Engineering
investments, there is also a new

T
window of opportunity opening he oil industry will always
for owners who are positioned to remember 2008 as the year
move their projects ahead. when oil prices exceeded
The high price of transportation Davio the $160/bbl threshold for the
fuel shook consumers in the first first time. Fortunately, we seem
half of 2008. Their reaction, reducing vehicle miles to be positioned once more for
travelled by 3.7% from 2007 and switching from SUVs and fundamentals to drive the market
pickups to more fuel economical cars, has caused a sudden and for product prices to again take
shift in fuel demand, particularly in the US. The economic a lead in establishing crude prices,
meltdown that followed has caused capital to dry up, since the refiner, as the voice of
share prices to fall and owners to move towards preserving the consumer and after covering
cash flow. While some projects are being scaled back his costs and customary profits, Guariguata U
and others are seeing their completion dates extended to will pass to the producer what
delay expenditures, most projects that have passed through he is willing to and can pay for the feed to the plants. This
their funding gate are continuing through the engineering is an obvious first principle concept, yet when exogenous
and construction phases. The challenge for owners is third-party players are present in the feedstock pricing
to determine which new projects to undertake and at mechanism, the market experiences what was lived in 2008,
what pace. when crudes prices were totally out of sync with product
We believe that owners who proactively move their prices, as confirmed by an article in the Washington Post
projects forward through FEED and then proceed to select that a single trading house had at one time more than
their EPC contractor will position themselves very well to 10% of all oil contracts on the regulated NYMEX. There
take advantage of favourable pricing for equipment, bulk were many others. What seemed a speculative comment at
materials and construction services in 2009 and 2010. At the first became reality and very unlikely to repeat itself in the
present time, equipment and material suppliers are near term.
experiencing strong backlog. A year ago, most would have So 2009 will be a year of tempered spirits, a mystified
predicted that this trend would continue for the foreseeable consumer and an industry that will again have to retrench
future, but it is apparent now that there will be a delay in — something it has done successfully in the past. The year
new orders, reducing the impacts of escalation and resulting will bring memories of the combined effects of market
in reduced pricing for some equipment and materials. funda-mentals and unilateral actions from OPEC on
How long this window will be available is difficult to petroleum prices. Are less than $2/gal gasoline prices
predict, as the long-term demand forecasts continue to supporting a less than $60/bbl average crude price with
suggest that the projects that have been recently delayed refinery margins profitable around a $9/bbl range, depending
will be needed and when the economy again strengthens on technology, indicative of a meltdown? Not exactly, they
they will be reinstated. are familiar territory that the industry has successfully
So owners who put their projects into a position to place weathered in the past. This environment should return the
orders for equipment and materials during 2009 will be able sector to sustained profitability, postponing some expansions,
to react when the market situation looks most advantageous yet likely keeping debottlenecking and maintenance
to them. This means getting equipment clearly specified programmes on track. This is a great opportunity to excel,
and completing engineering to a level that materials can be improve on operational efficiencies and re-educate the public
quantified, and ensuring execution plans for procurement, over the industry’s polluting and price-gouging image, with
low-cost sourcing, fabrication and construction are which it has been unfairly labelled in recent years.

www.eptq.com PTQ Q1 2009 7

 What are the obvious risks? It is a known fact that most of
the future oil reserves are in the hands of those countries
that have little sympathy for the governments and the “Companies that thrive in changing
majority of the people who consume it. This has been a markets, have cash and are patient are
strong driving force to reduce the dependence on oil all
together and to begin examining more seriously the perfectly positioned to take advantage of
possibilities of alternatives to electrical power generation the current downturn”
and hydrocarbon-powered vehicles, while preparing the grid
for more power from wind turbines and photovoltaic
cells. However, despite the omen of a few, oil will continue
to play an important role in transportation fuels for years to fixed on a handful of key indicators: the Michigan
come, but less so in other areas such as heating and Consumer Sentiment Index (MCSI), the Chinese GDP growth
power generation. rate, the price and production volumes of crude, the
The most recent US refinery data show yields in monthly number of new car sales, and a basket of stock
transportation fuels at 88%, of which half is motor gasoline market indices.
and one-third is distillate for automotive use and heating oil. A wide spectrum market consolidation will occur over the
The remainder is some residual fuel, speciality products and next two years. Companies that increased debt loads for
pet coke. So it is evident that refineries are not the main external growth will have a difficult time making it through
source of product for electrical power generation — that this downturn. Those who have cash are likely to keep what
honour belongs to coal and nuclear. A rapid move to wind they can and hunker down until visibility returns, and then
and photovoltaic cells will take time to develop. In the acquire weak prey. Groups in the refining, petrochemical and
interim, oil will still be relevant, and steps to reduce foreign engineering sectors have lost significant market capitalisation.
dependency while developing alternatives energies seem to The larger predators are already preparing to pounce on
be the right path — one that has been talked about often in undervalued competitors with oil and gas reserves (oil
the past and whose time has finally arrived. companies) or with specific engineering competencies for the
Unfortunately, alternative energy-producing technologies future, such as nuclear, wind or solar power (engineering
become less attractive when crude prices are low, so there contractors).
may be a need for government incentives to provide the The next two years will be interesting times — a
market drivers for projects to occur. Eventually, the consumer period from which the leaders of the future will emerge
will foot the cost of this market intervention. The crude in politics, in finance and in the petroleum industry.
producers, on the other hand, will continue to manage their We have the fortune to participate in this period of change.
resources with a criterion of scarcity while the petrodollars It is a chapter in history that will lead to a redistribution
significantly decrease. Some will become visionary about of cards and the creation of new industry kings, some
keeping their main resource viable and needed in times of of which will ride in from the east on steeds of sovereign
anticipated irreversible structural demand change, while wealth funds.
others will re-evaluate the merits of using energy as a Consumers are worried about their jobs. Thus, the
political means with oil funds, now significantly diminished acquisition of major non-essential goods, such as new cars
and most likely to remain so for the near future. In the long and appliances that contain plastics, will be largely foregone
run, crude prices will again raise as a result of postponed in 2009. Thus, a very poor petrochemical climate is expected
projects in the critical production areas. Some even argue with production turndowns, even with soft naphtha prices.
that they will again exceed the $100/bbl threshold, since Conversely, motor fuel consumption could rise compared to
also the consumer, fortunately for the industry, has shown 2008 due to the lower fuel prices. Speculation is that crude
in the past collective amnesia to these cycles and returns to should average around $80/barrel next year, which would be
their habits of uncontrolled consumption when transportation sufficient to continue most investment plans.
fuels remain inexpensive and the cycle again comes full Many refinery projects will be delayed either due to
circle. Hopefully, not on my watch. a lack of financing, for those without the cash, or expectations
of lower project costs. Steel demand and prices are
plummeting. Also, the unexpected short-term availability
of contractors is stimulating operators to reopen projects
Charles Cameron for competitive bidding. Cash-rich operators will
Marketing Director opportunistically advance new projects in the next three
to six quarters to maximise project value. Catalyst vendors
Axens may see some reduced operating rates in 2009 as new
capacities have come on-stream, but fuels specifications will

M
“ ay you live in interesting continue to be tightened, thus the future of the business
times” is a euphemism is sound.
that entered the English Refined product demand will pause for several quarters,
language circa 1936. It is an but will inevitably grow in the mid- to long term. The
appropriate description of recent same challenges remain: mid-term supply tightness, gasoline-
events, when the prices of crude diesel imbalances, bottom-of-the-barrel upgrading needs,
climbed from $50/barrel to over and fuel oil sulphur reduction. In the long term, there are
$140/barrel in 18 months, only to many challenges surrounding greenhouse gas emission
peak in early July and fall to $50/ reductions: carbon capture and storage, clean coal, second-
barrel in November. generation biofuels, the place for nuclear energy, and the
The next 12 months are implementation of a World-Wide Emissions Trading Scheme
unpredictable and depend on Cameron (WW ETS).
factors outside of a company’s Companies that thrive in changing markets, have cash and
control, in particular government stimulus packages, are patient are perfectly positioned to take advantage of the
OPEC’s reduction in production volumes and consumer current downturn. Enterprising groups that have the depth
sentiment. The “glass half-full” consensus is that an upturn to continue to invest for future challenges are well positioned
is unlikely until the second half of 2010. Keep your eyes for tomorrow’s growth markets.

8 PTQ Q1 2009 www.eptq.com

www.ptqenquiry.com
for further information
 energy initiatives required to meet the growing energy demand
Lou Pucher in an environmentally responsible manner.
President Yet it is also important to remember that despite the steep
decline in oil prices in recent months, it will ultimately remain
Shaw Energy & Chemicals Group at historically high levels. Cyclic trends periodically reduce
demand for fuels and petrochemicals, but as global population

A
s we enter 2009, we find and economies grow, so will related production and our
ourselves in a very different technology contributions.
landscape than a year ago. A
string of global economic upheavals
throughout 2008 has culminated
in one of the largest financial crises Carlos A Cabrera
in generations. Its effects, felt most President & CEO
immediately on Wall Street and
overseas stock markets, are rippling UOP, a Honeywell company
throughout every strata of our

T
society: from corporate boardrooms oday’s refining industry
to corner shops to the kitchen table. Pucher is confronted with a very
From a heady high near $150 challenging and dynamic
this past summer, oil prices have tumbled to $50 today. Early environment. It needs to be able
in 2008, high feedstock costs led to elevated world ethylene to profitably produce a variety of
prices, which have since returned to typical industry averages. products to meet growing demand,
The story is similar for propylene production. comply with ever-changing
As economic growth continues to slow, industrial production regulations and mandates, and
will be affected. We see some refiners and petrochemical accommodate unprecedented
producers deferring plans for grass-roots facilities and reducing volatility in feedstock costs and
current production. What other key concerns do we recognise product prices.
in our respective industries? Mandated environmental Some estimates suggest the Cabrera
initiatives, such as carbon capture and storage (CCS), will be world will consume 90–100 million
absorbing a greater share of a shrinking supply of capital, bpd of refined products in the next decade. The diesel-to-
putting more pressure on the funding of traditional capital gasoline demand ratio is poised to further increase and the
projects. The petrochemical and refining industry will have to demand for heavy fuel oil is expected to decline. At the same
account for higher costs associated with applying carbon time, prevailing environmental and political forces, in
capture technology to meet mandated requirements. general, remain hostile to the oil industry, making permitting
And what about plans to develop alternate energy sources for new facilities and expansions burdensome and virtually
— solar, wind and waves? Current low oil prices make these impossible in many regions, particularly in the US.
kinds of investments more difficult to justify, but we must In some areas where expansions and upgrades can be
anticipate eventual crude oil price recurrence. considered, capital is becoming increasingly scarce. The
Many oil company executives contend that the recent drop question becomes how can the industry increase yields and
in oil prices will make it more challenging to sanction the further optimise existing operations to reduce costs? To
projects required to meet future demand. Already projects in remain competitive, refiners and petrochemical producers
Canada’s oil sands and other major projects in remote, can focus on reducing energy consumption. Using novel
difficult areas are being delayed. However, many other processes, catalysts, adsorbents, equipment and automation
projects, including coal conversions, continue as planned. technology, refiners can realise up to 25% savings in energy
The immediate approach will be to develop technologies consumption and substantial reductions in carbon dioxide
that help us ultimately reduce our production costs. We are emissions.
investigating ways to improve operating efficiency and This carbon dioxide reduction is important, because
profitability of existing plants and find lower cost routes to looming on the horizon is the uncertainty of when and how
produce ethylene and propylene. For example, refining and additional government regulations on emissions will be
petrochemical technology experts are jointly developing ways enacted, and at what cost to industry. Global harmonisation
to produce olefins from catalytic cracking technologies and of sulphur, nitrogen, benzene and other contaminant content
olefin-rich refinery off-gas recovery. of fuels are expected to continue, bringing the need for
Many ethylene plants as well as FCCUs in the US and additional investment. We have found that most of these
Europe are now over 30 years old. We expect to see significant challenges can be met through combinations of solutions,
technology revamp projects of these older units aimed at ranging from technology and catalyst enhancements to
lowering feedstock cost, improving energy efficiency and deploying new technology aided by advanced process
reducing emissions. Expansion may well be an indirect benefit optimisation and automation.
of these changes, but will generally not be the prime reason To face the challenges posed by this rapidly changing
for the improvements in US and Europe. environment, another key area of focus is feedstock selection.
Propylene production can also benefit from the application As new sources of crude oil become more complex and
of new technology. Much of the planned steam cracker olefin expensive to produce and refine, we must be prepared to
capacity being built in the Middle East and Asia uses ethane as diversify our feed sources and modify existing facilities to
a feedstock, creating a shortfall of propylene as a by-product. process heavier and more contaminated feedstocks. Energy
Deep catalytic cracking (DCC) technology, which uses a security will play an increasing role in determining future
fluidised bed process to produce high yields of propylene investments in new technology and feedstock diversification,
product, can help eliminate these shortfalls. particularly as governments become increasingly active in
In uncertain times, there’s a tendency for companies to focus regulating and stimulating the energy sector. As noted earlier,
on fundamentals to improve overall operating efficiencies. And the projected increase in world demand is such that all
now, more than ever, we rely on the talent of our highly skilled sources of transportation fuels need to be considered.
engineers and technologists. Additionally, the industry should However, any regulatory framework developed — while
look to respective government organisations to support the stimulating alternatives — must ensure that the oil and gas

10 PTQ Q1 2009 www.eptq.com

 Tailored refinery solutions.
Grassroots or revamps, large or small.
Increased ROI through high complexity.
More value from heavy crudes.

Got a plan? We do.

For more information, email refining@kbr.com or visit www.kbr.com/refining www.ptqenquiry.com

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HE Mar08 REFINING indd 1 2/15/2008 1:09:05 PM

industry remains robust and capable of investing and the financial crisis began and we watched oil prices plummet
marshalling the resources to meet the daunting demand and demand pull back more than expected, the number one
challenge. This is particularly critical in the short term, as question clients ask is how long will the pull-back in demand
currently there is no viable economic substitute for petroleum last? If you look at how the world reacted to the events
in the transportation sector. during the Iranian crisis (1979–81) and subsequent events,
Biofuels will also play a role in the future. But we global demand did not reach 1979 levels until 1987–1988.
cannot pursue biofuels without careful thought and This time the market reaction may be different. In just
planning. Production of biofuels must be profitable, efficient under 12 months, we have gone from relatively high double-
and sustainable. Biofuel options that are fungible and digit prices for oil to triple digits, and now the question is how
compatible with conventional refinery products, and low oil could go in response to global demand. Some of the
maximise the use of existing infrastructure and transportation firms trading in oil that bet on $150–200/bbl oil are now
technology, should be the preferred choice. Major challenges betting on $20–30/bbl oil (somewhat of a self-fulfilling
remain in developing the technology and the infrastructure prophecy). How quickly will consumers resume typical driving
required to enable investments of the scale required for patterns and bring back demand? Firms that were not
biofuels to make significant impact on the world supply of positioned to handle sharp downturns in the 1980s are now
transportation fuels. Additionally, feedstocks that displace able to quickly shed resources and position themselves better
arable land required for the production of food or require for either an extended downturn or a quick recovery. Consumer
deforestation are not sustainable or environmentally reaction over the next six months will dictate the market
desirable options. response for the downstream sectors.
Heavy tar sand-derived synthetic crudes are another Our outlook for 2009 focuses on two major themes:
source we must look to as we prepare to meet increased — The hydrocarbon industry response to demand loss
demand. Today, there are ongoing developments of — Environmentally driven issues: renewable fuels, greenhouse
technology to economically and efficiently maximise yields gas regulations.
from these heavier, more contaminated feeds. Shale oil is The international refining picture for the past several years
another option; however, it will require considerable infusion has been one of new capacity announcements, with a guessing
of new technology to be competitive with existing fossil game of which project gets funding and support to move
sources of transportation fuels. The attractiveness of the tar forward. Our list of project announcements has grown over
sands and shale oil is their abundant and untapped supply the past few years from 20 million bpd to almost 30 million
potential, which is comparable in magnitude to known bpd as companies and countries issued press releases. However,
reserves of crude oil. as we review each project by its sponsor, location, past history
It is clear that new technology is the key to our energy of success, the realistic numbers for capacity expansion
future, and nowhere is that more apparent than for through mid-decade has consistently fluctuated between 9–11
transportation fuels. Closing this technology gap to someday million bpd. With the credit crunch, our expected additions
replace petroleum-derived transportation fuels requires are now solidly on the lower end of the range.
substantial invention and innovation. Well-educated and The demand loss and credit crisis has also given a number
experienced scientists and engineers, in short supply today, of major projects the opportunity to take a time-out and put
are critical to this success. In 2009 and the years to follow, pressure on procurement and contracting for lower price tags.
the industry will face significant challenges in securing Several of the Saudi projects fall into this category, where bids
experienced talent. As veteran workers retire in record will be delayed until mid-2009, with a major stated objective
numbers and college graduates are hired to take their places, to drive down costs. This is happening in both upstream and
we must place strong emphasis on training, knowledge downstream project investment.
management and optimised practices throughout the plant As highlighted in prior outlooks for PTQ, a major driver for
lifecycle. We must capture the knowledge of experts and put much of the large US investment has been tied to projects for
it to use broadly and effectively. processing Canadian oil sands. Motiva Port Arthur, Marathon
We have faced severe challenges before and our industry Garyville, BP Whiting, ConocoPhillips Wood River, and
always seems to find economic, sustainable and viable Marathon Detroit fall within this group. The cost and financial
solutions. It is no different this time. Government actions issues, however, have led to several of these projects slowing
that allow the marketplace to determine economical and down their spending and delaying project execution. Along
efficient solutions will, in the long run, bring the greatest with the slowdown on the US side of the border have been
societal and economic benefit. Ensuring a level playing field project cancellations or delays in Canadian projects. Petro-
will determine the true winning solutions. Canada Fort Hills, Total and Statoil have all delayed or deferred
major capital decisions or spending due to rapidly escalating
price tags for projects. Other synthetic crude oil producers
such as Suncor, Syncrude and Canadian Natural Resources
Karl D Bartholomew Limited have decided to delay later phases of projects.
Director The loss in demand presents as significant a challenge, if
not bigger, in petrochemicals. We are already seeing substantial
Jacobs Consultancy drops in facility utilisation, from our own survey services such
as the Hodson Report for ethylene crackers as well as

C
oming up with a coherent announcements of plants being idled (BASF, Equistar and
outlook for 2009, given the Nova) to facilities being shut down entirely (Flint Hills
upheaval we are currently Odessa). The feedstock supply chain in the Middle East and
seeing in this last quarter of Asia is particularly sensitive to the loss in demand growth, as
2008, will be a challenge for any much of the market is export driven.
forecaster. One suggestion is to see Even with the market challenges, companies continue to
how the industries and markets look at smart investment opportunities. As crude oil prices
reacted to past events. At mid-year, retreat to levels more in line with natural gas feedstocks, those
our outlook for clients and our own US facilities with flexibility in feedstock selection may now
management focused on capital have an advantage over investment spending in light feed
cost issues and concerns on demand projects. However, these facilities will still be at a competitive
reduction due to high oil prices. Since Bartholomew feedstock disadvantage to the Middle East crackers.

12 PTQ Q1 2009 www.eptq.com

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 The next game-changing event for the process industries
will be the implementation of greenhouse gas/climate change “We are optimistic that 2010 will see a
regulations. The refining sector is focused on how the GHG
regulations will tie into the Renewable Fuels Standards (RFS 2) strong recovery in oil demand growth,
required by the Energy Independence and Security Act of which will be maintained for much of the
2007 (EISA 2007). At the time this column was written, how
many issues will be addressed is still unknown. We do know following decade”
that including indirect land use for corn-based ethanol
substantially increases its impact on the environment in a
negative (not positive) manner. With oil prices increasing, motorists voted with their wallets.
The refining industry will be challenged to meet increased For example, in the US, sales of SUVs sank like a stone and
volumes of renewable fuels in the gasoline pool as a result of consumption of gasoline fell by 8% versus last year. Similar
the EISA 2007 mandate as well as determine how to reconfigure declines in demand became the norm throughout the
their hydrocarbon fuels to offset ethanol’s impact. Companies developed world. A new phrase, “demand destruction”,
will also be learning how to develop their GHG inventories as came into being. Just as our attention switched from
we move from voluntary reporting to mandatory reporting. worrying where the supply was coming from to worrying
As our own firm moves through the process of ANSI (American where demand had gone, Saudi Arabia, in a masterpiece of
National Standards Institute) certification for GHG auditing timing, reacted to months of pressure as prices rocketed by
and verification, it is easy to see that developing a verifiable announcing increases in oil production totalling more than
inventory will become a major learning curve for those in the half a million barrels per day.
industry who have not yet looked at their carbon footprints. Within 80 trading days, the price of oil fell from $147–60/
The lack of climate change standards is frequently cited as bbl. Incredibly, from looking for the price ceiling, we are now
a major reason (along with escalating capital costs) why searching for the price floor. Instead of the OPEC countries
gasification projects are not making as much progress as once producing oil at full capacity, they are now scrambling to
anticipated. A colleague in the project finance community has make production cuts in an effort to shore up the price. At an
several projects unable to progress — the main reason stated October 2008 emergency meeting in Vienna, OPEC announced
is the uncertainty in how CO2 will be handled, either by a cap 1.5 million bpd of production cuts and, for the time being,
and trade programme or by carbon tax. this move has helped to stabilise the market.
In October 2008, the International Maritime Organization The issue now is discovering the consequences of such a
(IMO) adopted the MARPOL VI (Marine Pollution) standards massive cut in prices; where are prices headed in the short and
for maritime ship emissions. The deadlines and effective medium term? The consequences of $60/bbl oil are many and
sulphur limits are now known: by 2015, those ships moving varied. First, they bring relief to consumers in the developed
through Sulfur Emission Control Areas (SECAs) will be world faced with high heating and transportation bills;
required to burn the equivalent of 0.1% sulphur marine fuel. second, they disrupt the best-laid budget plans of the OPEC
The European Union had already signed onto the MARPOL VI countries; and third, they raise doubts about the viability of
standards; the US has now done the same. The globally critical projects both upstream and downstream.
deadline is 2020, where all ships in waters except in SECAs The first issue is critical to the economic health of the
will have to use the equivalent of 0.5% sulphur fuel. developed countries. Lower oil bills might help kick-start
Implementing MARPOL VI is not straightforward. At first, economic recovery; however, consumer confidence is so low
it would appear adding fuel oil conversion capacity and that little immediate benefit will be felt. If $60/bbl becomes
hydrotreating to produce lower sulphur marine distillate is the norm, there will eventually be a boost to oil demand.
the answer. Some parts of the shipping industry see this as the The second issue of OPEC’s budgets is very intriguing. It is
proper outcome. Other participants believe the price tag for widely held that a price of $75–95 is required to meet the
marine distillates will be too high and on-board scrubbers are cost of developing new sources of oil and the needs of social
the right answer. The scrubbing solution for MARPOL VI has programmes of certain OPEC countries. The third factor —
not been fully vetted with regards to the technology or the the viability of projects — is of profound importance for the
costs. A concern that we believe will come to the forefront will direction of oil prices in the long term. It was widely reported
be how ships will handle the scrubber wastes. Putting the that Total Petroleum requires an oil price of $90/bbl to
scrubber effluent back into the ocean will likely face strong achieve a 12.5% internal rate of return (IRR) for its Canadian
challenges from environmental interest groups. We believe tar sands project and a $70/bbl price to achieve the same IRR
this dynamic will become clearer in the next couple of years. for its deepwater production project in Angola. Many other
projects also carry a high cost structure and must be at risk
from $60/bbl oil. In the downstream sector, before the
economic crisis engulfed us all and destroyed demand, we
George Bright were faced with a wave of new refining capacity coming on-
CEO stream that exceeded oil demand growth by a factor of
nearly three. Too much refining capacity facing too little
KBC Advanced Technologies demand growth spells poor refining profitability. The
essential point is that investors, faced with lower crude oil

T
he recent financial and prices and declining oil demand growth, are starting to defer
economic gloom has or cancel both production and refining projects, thus storing
gradually created today’s up the prospect of future shortages of capacity when oil
mood, in which it is widely demand growth eventually recovers. In refining, we see
accepted that we are in a recession marginal refining capacity being shut down in both Europe
that could develop into something and the US and increasing pressure on margins as new
worse. The oil price has been a capacity comes on-stream in Asia. We would expect a return
direct casualty of the crisis. In the to the sentiment of the 1980s and 1990s, with an absolute
first half of the year, the accepted focus on cost minimisation.
view was that global GDP and oil Having laid out the possible consequences of prices at $60/
demand were growing satisfactorily bbl, what does KBC think will actually happen to prices? In
and there were strains in oil supply. Bright the very short term, we believe that OPEC will succeed in

14 PTQ Q1 2009 www.eptq.com

www.ptqenquiry.com
for further information
stabilising the oil price with production cuts; as a result, in challenge for Emerson and other suppliers is to learn more
2009, the average price of Brent crude oil will be $80/bbl. We about these government-owned firms and their business
are optimistic that 2010 will see a strong recovery in oil practices so we can help them compete globally.
demand growth, which will be maintained for much of the In the US, the lessons learned during the 2005 hurricane
following decade. season by refineries and their partners meant hurricane Ike
While this all seems perfectly logical, the problem is that had much less of an impact on refining in September 2008.
inside of three months we have seen prices fall by nearly $90/ While there was significant short-term loss in refining
bbl. So, how on earth can we be sure the same thing will not capability, for the most part those refineries were back on line
happen again, this time in reverse? We cannot. quicker than in the past. That improved ability to respond to
threats will serve the industry well in 2009 and beyond.

Steve Sonnenberg
President Don Clark
Vice President, Global Industry Solutions
Emerson Process Management
Invensys Process Systems

T
he high cost of doing

T
business and a worldwide he future of petroleum
economic slowdown will refineries and petrochemical
pressure petroleum refiners to plants will be significantly
operate more reliably and impacted and affected by their
efficiently in 2009. need to reduce carbon emissions.
While the stalled economy and Refineries and plants will
erratic financial markets probably accomplish this primarily by
will not affect ongoing refinery reducing their energy consumption
expansion and modernisation and carbon sequestration, and
projects, refiners may decide to they will rely on advanced
proceed more slowly with new Sonnenberg process automation and control
projects now in the conceptual technology to achieve this. Clark
phase. The crisis in the economic investment world has Dwindling availability of light
thrown companies a curve ball, and they are reacting to that conventional crude oil has created a growing demand for
with caution. clean fuels refined from alternative crude sources. Oil sands,
Today, refiners’ profits are continually squeezed by a oil shale, coal and natural gas will become increasingly
combination of reduced market demand for their products important fuel sources. While this is good for oil importing
and crude price swings “on the front end” that challenge their countries, it will require new capital investments to upgrade
ability to get profits “on the back end”. When operating costs refineries so they are able to handle these liquids, or synthetic
remain high and demand goes down, refiners must consider crude oils, that have significantly different chemical properties
new ways to cut costs and avoid process slowdowns and than those of conventional crude oils.
shutdowns. The best use of technology can address these As vehicle fuel economy improves, primarily due to
challenges by allowing companies to gain reliability and government mandates and consumers’ desire to reduce their
efficiency. own CO2 emissions, and as baby-boomers retire and the use of
Wireless devices can collect data about plant processes and renewable fuels increases, demand for petroleum-based fuels
assets throughout the facility, including areas that were will slow. As a result, petroleum refiners will be challenged, at
previously inaccessible. Many refiners, including one of the least in the near term, to maintain profitability.
world’s largest energy producers, have worked to test and In the US, demand for diesel fuel is expected to grow
establish numerous wireless applications. The ways wireless steadily, somewhat offsetting the decline in gasoline demand.
can be applied to cope with today’s challenges and improve This forecast is predicated on changes in demographics and
refining operations are limited only by the creativity the composition of the vehicle fleet. Over the next decade,
of the user. diesel production per barrel of crude is expected to grow to
A long-time industry challenge that will continue into the 30% from the current yield of 20%.
new year is the shortage of adequately trained refinery A slowdown in China’s economic growth will put pressure
operators and other skilled employees. As senior staff members on petrochemical producers, since demand for consumer goods
retire, companies cannot hire knowledgeable, experienced will also slow. Emphasis will be placed not on maximising
personnel to take their place. For some companies, finding production, but on minimising operating costs. As with energy
qualified employees is their largest expense, such as in the oil management, advanced automation and control technology
sands of Calgary, Canada, where refinery personnel are flown has proven to be a cost-effective means of managing plant
in regularly for each work shift from Atlantic Canada and the economic performance. For example, recent initiatives taken by
interior of British Columbia to the work site. Sasol, a South African company involved in mining, energy,
Significant world events often influence the refining chemicals and synthetic fuels, have shown that substantial
industry, and it will be no different in 2009. During the last reductions in variable costs can be achieved, with little to no
few years, government-owned oil companies, such as Petrobras capital investment, simply by giving operators real-time
in Brazil, Petroleos de Venezuela in Venezuela and Gazprom in information about the economic impact of their decisions and
Russia, have begun to produce enough oil to not only supply permitting them to take action based on this information.
their countries’ needs, but to export crude and refined To better leverage technical expertise and reduce support
products to the world market. These national oil companies, costs, multi-site refining and petrochemical companies will
part of a group called the New Seven Sisters, sit on 80% of the increasingly centralise their operations centres, which will
world’s oil reserves and wield a market force greater than the facilitate teamwork and collaboration by bringing operational
industry’s original Seven Sisters (Amoco, BP Chevron, Exxon, and technical issues and problems to the experts rather than
Mobil, Shell and Texaco). This new breed of oil company will requiring the experts travel to the site. This too will rely on
redefine the oil business for the next several decades. The advanced process automation and control technology.

16 PTQ Q1 2009 www.eptq.com

www.ptqenquiry.com
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 Processing trends
Outside of the realm of traditional refining processes typically discussed in PTQ are
developments equally important to the diversification of transportation fuels and
petrochemical product sources. Market volatility and fluctuations in feedstock costs compel
the industry to continuously reassess viable process scenarios in GTL and olefins processing

Converting natural gas into liquid fuels currently being flared. The liquid product is also flexible, since
On again, off again: when is gas-to-liquids (GTL) ever going to it can produce either diesel, 95 octane gasoline or ethylene.
become competitive? Efforts continue in the development of One of the major deterrents to widespread development of
a cheaper and cleaner way to convert natural gas into gasoline world-scale GTL projects in the past has been the high capital
and other liquid fuels, making it economical to tap natural gas costs of such ventures. However, the rapidly increasing price
reserves that in the past have been too small or remote to of a barrel of crude, touching new highs of $100, and the
develop. For example, there have been efforts at developing a emergence of new technologies to drive down costs, as well as
process that involves fewer steps and is more efficient than the employment of economies of scale — such as the Pearl
the more established techniques that are based on the Fischer- GTL and Oryx GTL projects — all serve to indicate that GTL
Tropsch (FT) process. However, if such a process works well, it projects could soon emerge at the forefront of the alternative
will no doubt drive up the price of natural gas as more natural energy and fuel markets, provided crude prices again escalate
gas gets used to produce liquid fuels for transportation. That to above $100/bbl from the $50/bbl in December 2008.
will, in turn, reduce the desirability of natural gas for use in Otherwise, as GTL trends veer towards small to mid-sized
heating and electrical power generation. projects, there is a critical need to drive down capital costs to
A better way to convert natural gas into liquid fuels, accommodate smaller investors. The viability of small-scale
according to some developers, is by using small chemical projects is being considered. For example, the proprietary
plants that would allow many smaller and/or remote natural Microchannel process technology developed by Velocys may
fields to be tapped. For example, natural gas on the northern have a role to play in terms of reducing the size and cost of
slope of Alaska has not yet been exploited because the costs of GTL projects.
building a natural gas pipeline to bring it down to the lower Commercialised FT technologies combined with the more
48 states is quite high. Therefore, if there was a way to convert traditional cost reduction strategy of catalyst recycling also
the Alaskan natural gas to liquid form, this would allow the help make existing FT technology more competitive with mid-
existing Alaskan oil pipeline to move the liquid south. sized projects. For example, Umicore AG & Co KG, one of the
A start-up company in California, Gas Reaction Technologies, companies fronting catalyst recycling technology, can help
claims its GTL technology will work well for medium- and add more value to FT-based processes and increase planning
small-sized natural gas fields. If such technology indeed lowers reliability. With certain segments of industry now using GTL-
the cost of GTL, then why use natural gas as a vehicle fuel when based kerosene (eg, Qatar Airways) instead of the traditional
it can be converted to a far more convenient liquid form? But crude-derived jet fuel or kerosene, the demand and potential
since the conversion itself uses energy, natural gas converted to for the GTL-derived liquid fuel market may be set to expand.
liquid fuel represents a loss of energy that would not occur if
natural gas was directly burned in cars. This is the reason for Ethylene-based trends in North America
scepticism that there will ever be a big shift to natural gas for Ethylene, as the largest-volume petrochemical in the world, is
vehicle transportation, as there is apparently a trend (albeit often used as a benchmark to measure industry competitiveness.
gradual) towards more efficient and less costly GTL technology. It is a particularly important petrochemical for countries such
Liquid fuels are more convenient and use up less space. as Canada because so much of its chemical industry is ethylene
Technological developments that cut costs for achieving the based. However, the Middle East is easily the world’s lowest
natural GTL conversion will provide a more convenient and cost producer of ethylene. It derives that advantage from very
therefore more valuable way to use natural gas. low prices for ethane feedstock and natural gas energy, but this
However, sceptics on the other side of the argument predict cost advantage is beginning to erode. New Middle Eastern
that small chemical plants using non FT-based technology for contracts for natural gas and ethane will not be priced as
capturing remote pockets of natural gas into liquid fuels will advantageously as former contracts were. The supply of
probably never be built on a commercial scale considering the incremental ethane is also becoming constrained, forcing
current financial and credit crisis. They will be too risky to some new cracker projects to utilise heavier feedstocks like
build at the scale needed to make it viable. Another important propane, butane and naphtha.
reason is that natural gas to LNG is around 90% efficient on a The province of Alberta in Canada is the second lowest cost
carbon basis compared to the claimed 50% for this proposed ethylene-producing region in the world. Alberta derives its
non-FT technology. In any event, methanol manufacture competitive advantage from a number of factors, including
from natural gas is around 70% efficient for specifically the fact that the price of North American natural gas has been
defined circumstances (eg, world-scale size rather than small compared to crude oil. Ethylene crackers based on natural gas
or modular scale), so if an investor wants to make liquid fuels liquids are advantaged compared to crackers based on crude
from natural gas, methanol may be the way to go, as methanol oil-derived feedstocks like naphtha. Ethane is also less
technology is already proven at scale. expensive in Alberta than on the US Gulf Coast due to the
To be sure, non-FT technology developers have never regions’ differing market dynamics. The ethane-extracting
claimed to have superior efficiency compared to FT technology plants in Alberta are very large and offer economies of scale.
or other concepts that have been patented. They only claim Finally, the ethylene crackers are large and modern and offer
to be more efficient than FT on much smaller scale applications additional economies of scale. Historically, Alberta producers
(ie, monetisation of remote pockets of stranded gas). So, have a cost advantage compared to the US Gulf Coast of about
small-scale non-FT technology would be ideal for the six cents per pound of ethylene.
conversion of gas reserves that are too far from the market or Work has been under way under the auspices of the

www.eptq.com PTQ Q1 2009 19

 Hydrocarbon Upgrading Task Force in Alberta for several years Currently, pyrolysis technology can co-produce ethylene
to promote the concept that products and off-gases from the and propylene in ratios of around 1:0.5–0.6. Since, until
processing and upgrading of oil sands should be utilised recently, the demand for propylene-derived products had
within the province to produce refined petroleum products been very strong, the traditional co-production of ethylene
and petrochemicals. The motivation is to extract maximum and propylene via refinery recovery methods would not be
value added from the bitumen resource for Alberta rather than enough to fulfil future demand. When the demand for
exporting raw materials. At production levels of two million propylene again exceeds 4.5% per year, as it is expected to in
bpd of bitumen, exporting raw bitumen contributes about $25 2010, catalytic technologies more than likely will have been
billion per year to Canada’s gross domestic product (GDP). If improved. This includes improvements to the traditional
the bitumen is upgraded to synthetic crude oil, the GDP steam pyrolysis and catalytic technologies, such as propylene
contribution doubles to $50 billion. If the upgrading continues production based on catalytic cracking technology
downstream to refined petroleum products and petrochemicals, (eg, DCC), along with ethylene plant support technology
the GDP jumps to $75 billion or higher, depending on how far such as butene disproportionation technology and C4/C5
down the value-added spectrum you go prior to exporting a cracking into propylene.
product. Achieving this vision will require significant new Asia’s propylene production capacity of 24.269 million
investments in refinery and petrochemical capacity. tonnes/year makes it the largest propylene-producing region
in the world, representing 32.4% of the world’s total production
Olefins market and technology trends capacity. In 2005–2010, ChemSystems projects world
A recently released Nexant ChemSystems study, Petrochemical propylene production capacity to increase by about 18 543
Market Dynamics: Olefins, provides detailed projections on the million tonnes/yr. World annual propylene production
olefins market, including ethylene, propylene and butadiene. capacity will reach 96 804 million tonnes in 2010 and 108 653
While demand for olefins such as propylene had been increasing million tonnes in 2015.
by at least 5.5% for the past several years up until the beginning The trend in ethylene and propylene production technology
of the financial crisis last September, the next few years will see and materials is moving in the direction of diversification and
a tempering of propylene demand. Already, certain naphtha- the development of new technologies. Ethylene crackers now
based steam crackers, such as one on the US Gulf Coast, have tend to use lightweight materials, and many manufacturers
shut down indefinitely due to low propylene demand. However, try to optimise the cracker unit to produce more ethylene,
it is expected that long-term demand beyond 2010 will be and this is bound to reduce the volume of propylene
significant. Apart from steam cracking, FCC processing (eg, cogeneration in steam cracking.
deep catalytic cracking [DCC]) and traditional production 2008 now seems certain to be the turning point for olefins
techniques, propane dehydrogenation and translocation such as propylene, with major new plants already on-stream,
reaction mechanisms are developing, and gas hydrocarbon and the economic outlook looking decidedly weaker. Margins
technology has also been considered a viable technology. have been disappearing from much of the olefin value chain
in 2008, as lengthening markets prevent producers from
passing through rising feedstock costs.
It is against this background that the ChemSystems olefins
report investigates the market and growth profile for olefins
such as ethylene, propylene and butadiene, and details the
expected developments in supply and trade. The report finds
that 2008 will mark the end of the period of high operating
® TM
rates, which now start their decline towards a trough expected
in 2011–12.
Global propylene growth has averaged 5.5% over 1995–
CO 2007, and is expected to slow down to 4.5% over 2007–2015.
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focused on the Middle East and Asia, with the former taking
Real Time Performance Management advantage of low-cost feedstock, and Asia exploiting
for the Enterprise proximity to market, refinery developments and fixed cost
www.osisoft.de advantages. In a high oil price environment, feedstock cost
is a primary driver of competitive advantage. The new plants
IDC in the Middle East had been exploiting this advantage to
supply derivative markets in both Europe and Asia, and will
Industrial Data Center prove a significant threat to established suppliers whose
www.wiredcity.com economics are based on naphtha, such as European steam
WiredCity - an OSIsoft Company crackers. It is these naphtha-based producers, who until
recently enjoyed high operating rates and good
OSI SOFTWARE GmbH export demand, that will suffer most during the trough
Hauptstraße 30 • D-63674 Altenstadt • Germany
in 2011–12.
Phone: +49 6047 9890
The ChemSystems study notes that a major shift in trade

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20 PTQ Q1 2009 www.eptq.com
patterns for ethylene derivatives is also anticipated. in the Middle East. On-purpose propylene production has
Polyethylene expansions in the Middle East are projected to therefore become increasingly important in meeting demand
exceed the import requirements in China and the wider growth. The proportion of propylene produced from on-
Asian market. Regions such as North America and Western purpose processes is forecast to increase from 5.0% in 2007 to
Europe will therefore have to absorb a substantial increase in 12% in 2015.
net imports. Global growth of propylene consumption In geographic terms, propylene is surplus in North America
remained strong in 2007, reaching 73 million tonnes. as a result of the large refinery capacity and preference for FCC
Polypropylene, accounting for 62% of propylene demand, is units. Only 2.0% of propylene produced in the region was
among the fastest growing commodity polymers. A significant derived from on-purpose processing in 2007. The scarcity of
change in polypropylene trade positions is expected as the propylene in Western Europe, particularly in Germany, has
Middle East emerges as a major exporter of polypropylene. meanwhile seen very strong margins for the two propylene
Operating rates among less competitive producers in western dehydrogenation (PDH) units operating in Europe and
countries will be depressed, with Asian producers protected investment in a metathesis unit.
to some extent by soaring regional demand. The global Diversification policies in the Middle East have to some
butadiene markets have also been tight due to inadequate extent shifted attention to propylene derivatives rather than
investment in new capacity, contributing to record price ethylene derivatives in the region. Several new world-scale
levels. The rapidly developing automotive manufacturing cracker complexes are now equipped with metathesis
industry in Asia, particularly China, is one of the major units. There has been a lot of interest in combined PDH/
drivers affecting butadiene globally. Major steam cracker polypropylene units to fill the short-term supply gap for
developments in Asia will result in increased mixed C4s for polypropylene, but less activity is expected in the longer term.
butadiene production and a reduction in operating rates Propane will instead be consumed in ethane/propane-based
towards 2011. In the long term, the growth of ethylene steam crackers.
production, and therefore the availability of C4s, will exceed In Asia Pacific, heavy-liquid steam crackers are a major
demand growth for butadiene, leading to increased source of propylene supply. Around 8.0% of propylene in the
reprocessing of steam cracker C4s. region was produced from on-purpose units in 2007. The
In 2007, 115 million tonnes of ethylene was consumed availability of advantaged ethylene derivatives from the
globally. Polyethylene accounted for around 60% of global Middle East will limit the potential for ethylene capacity
demand. The next largest use is in the production of ethylene development in Asia Pacific, and so also limit the availability
oxide, primarily for the production of ethylene glycol. of co-product propylene. As most new refineries in Asia are
Growth in the vinyls chain is forecast to remain high owing opting for hydrocrackers to upgrade heavy oil fractions, FCC
to the construction boom in developing regions, although propylene opportunities will also be limited. On-purpose
the effect on ethylene demand will be diluted by the ongoing technology, particularly olefin conversion, is therefore
growth in supply via acetylene routes in China. Propylene expected to play an important role in propylene supply in
demand growth has historically been above global GDP. Asia Pacific.
ChemSystems projects that growth going forward will align
more closely to GDP levels. Growth in a number of derivative
markets such as acrylonitrile, cumene and acrylic acid has
slowed significantly. Polypropylene growth has also slowed
from the impressive 7.0% seen over the last ten years,
projected to be ongoing at over 5.0%. Increased penetration
into other polymers markets such as polyethylene and
polystyrene will be supported by increased propylene
availability. Butadiene prices have broken records each year
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since 2004, reaching over $3000 per tonne in Asia in mid-
2008. The peak follows long periods of oversupply for both
butadiene and synthetic rubbers. The Asian market has been
particularly attractive for butadiene producers due to the The New Generation –
ongoing development of car and tyre production in
the region. For More Safety
The proportion of ethylene capacity based on advantaged
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sustained period of high operating rates since 2004 has
masked this underlying change to regional competitiveness.
The impact of these new producers will become increasingly
clear as global operating rates decline.
In 2007, approximately 15 million tonnes of ethylene was
produced from ethane crackers, accounting for 14% of global
production. This number is forecast to nearly double by 2015, Low water Low water
showing the strongest growth across all cracker feedstocks. absorption absorption
The proportion of ethylene made from mixed-feed crackers is
also expected to increase, driven by rapid expansion in China. Catalyst Catalyst
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In contrast, naphtha’s share of global production will decrease toxin free toxin
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of propylene, which is usually not economically viable to P.
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552, DD -- 56225
56225 Ransbach-Baumbach,
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thus declining as a result of the major ethane-based investments

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PTQ Q1 2009 21
 cut deep should not be surprised
when the HVGO product MCR is
over 2 wt% and the vanadium con-
tent is in excess of 10 ppmw. Any
one of such difficulties can result
in lower revenue, unstable opera-
tion or even an inoperable unit.
It is critical to understand that
the inherent properties of these
low API gravity crudes dictate
that exact process design is of
paramount importance.
The point of this litany of possible
problems is to remind you not to
skimp in the early phases of engi-
neering. From the start of the LP
work through the completion of
front-end process engineering,
actual product yield and product
Nasty Stuff This exchanger has seen better slates. qualities depend on the process
design.
Heavy crudes are here to stay. Whichever the case, however, an The message is clear. Nasty crudes
As longs as oil prices remain high, inescapable fact is that the process will continue to make up an in-
Canadian, Venezuelan, Deep Water design of the project will prove creasing proportion of refineries’
Gulf of Mexico, Mexican and crucial. Between the charge pump crude slates. But time is precious.
other low API gravity crude oils and the desalter and the units’ dis- The sooner we face this fact,
will play an ever more important tillation columns there are many unwelcome as it may be, the more
role in supplying world refineries. places where miscalculations in expeditiously we can adapt.
And prices promise to remain high the process design could wreck the
because gainsayers notwithstand- entire project.
ing, Hubbert was right.
Can you really be sure of attaining
A big question is how to handle desired crude rates? Desalting vis-
best these nasty crudes? Do you cous crude is extremely difficult.
revamp existing units or invest Minimizing coking or asphaltene
in new capacity? With refineries precipitation in the heaters demands
now running flat out, the bal- extreme care. Can you reasonably
ance might seem to favor grass expect high diesel and HVGO
roots expansion, but given the recoveries, acceptable levels of
substantial cost multiplier over nickel, vanadium, and microcar- For a more in depth review, ask for
revamps, this could be questioned. bon residue (MCR)? Refiners who Technical Papers 173, 185 and 197.

PROCESS 3400 Bissonnet

Suite 130
Ph: [1] (713) 665-7046
Fx: [1] (713) 665-7246
CONSULTING Houston, Texas 77005 info@revamps.com
SERVICES,INC. USA www.revamps.com

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for further information
 ptq&a
The following are responses to questions concerning important processing issues in the
refining and petrochemical industry. Additional Q&A can be found at www.eptq.com/QandA.
PTQ wishes to thank all those respondents who have contributed both here and online

❝ For many crude/vacuum distillation units, up to

20–30% straight-run diesel gas oil can be found in catalytic
feed and thus become downgraded in the fluid catalytic
— Inclusion of separate pumparounds, draws and side steam
strippers for straight-run kerosene and heavy straight-run
diesel gas oil, so that the overlap of kerosene and heavy diesel
cracker. How can straight-run diesel gas oil be reduced in gas oil is appropriate, while the kerosene flash point is
catalytic feed to, say, 10%?
❞ enhanced (perhaps to >123ºF)
— Inclusion of heavy atmospheric gas oil pumparound,
draw and side steam stripper
Alan Goelzer, Senior Consultant, Jacobs Consultancy, alan. — Parametric optimisation of stripped heavy atmospheric
goelzer@jacobs.com: When the heavy atmospheric gas oil, gas oil (HAGO) volume percentage on crude slate, not zero or
vacuum diesel, light vacuum gas oil and heavy vacuum gas oil too small and not too high
composite within catalytic feed is analysed via GC-based — Use of inlet diffuser in the atmospheric tower, plus
simulated distillation (ASTM D6352), it is not uncommon to carefully selected hardware and number for the bottoms
find more than 20 wt% of the components exhibiting normal stripping trays
boiling points below 662ºF/350ºC. FCC riser reactors, operating — Optimisation of pounds superheated stripping steam per
catalytic and hot at 977–1022ºF outlet, within today’s fluid barrel of atmospheric tower bottoms. Superheat levels in the
catalytic crackers will crack most of these diesel gas oil 700ºF± range are recommended.
components into olefinic C3 and C4 LPG and FCC gasoline. Within this configuration, the vacuum diesel pumparound
The contribution from the light cycle oil (LCO) could be on and draw in the vacuum distillation unit are not a diesel
the order of the diesel gas oil’s polynuclear aromatics content, blendstock. Rather, the VDU vacuum diesel pumparound is
and this LCO will be extremely aromatic, with low API gravity structured to sustain and stabilise the target “vacuum”, and
and low cetane values. vacuum diesel is the first candidate to go to the co-processing
What happens to the diesel gas oil component is more hydrocracker unit.
complicated in FCC riser reactors operating cold at 950–968ºF. Within the context of revamps to existing crude/vacuum
If the catalytic feed assays organic hydrogen-rich and the distillation units, there can be constraints and challenges that
diesel gas oil more so, it can appear that the diesel gas oil has force some loss of volume percentage or BPSD out of the
undergone only partial cracking and boosted the API gravity heavy diesel gas oil. For example, previous revamps may have
and cetane values of the LCO. In any event, the LCO remains shifted the crude atmospheric tower to deep-cut lift into the
far inferior to the original diesel gas oil when ultimately HAGO to unload an undersized vacuum distillation unit. This
making ULS 2-D on-road diesel fuels or sulphur-free Euro IV drags more diesel components into the catalytic feed pool. In
diesel gas oil. other instances, the HAGO pumparound, draw and side
For more and more refiners, there are an increasing number stripper are missing, so the higher boiling fraction and the tail
of incentives to enhance the volume percentage output of of the heavy diesel gas oil see the original flash, along with
ULS 2-D on-road diesel fuels, while trimming back the output increased prospects for asphaltenes and metals.
of ULS gasolines and reformulated gasoline blendstocks for
oxygen blending (RBOBs). Increasing the volume percentage
yield of heavy straight-run diesel gas oil off the crude
atmospheric tower by lowering the 662ºF boiling point
components in the catalytic feed can be very helpful.
❝ At what point does a two-stage reactor design
significantly enhance HDS/HDA catalyst effectiveness
(considering recent efforts to process solvent or distillate
For a new crude/vacuum distillation unit, a combination of feedstock)? With current budget constraints, what
computer simulation modelling, engineering judgment and factors should justify the implementation of counter-current
minor incremental capital costs for optional extras can reactor technology over conventional co-current reactor
maximise the volumetric partition into heavy diesel gas oil
and away from the catalytic feed.
It is very important to establish the specification
technology?
❞
requirements with respect to maximum allowable values for Jesper Rødtjer, Sales Manager, Haldor Topsøe A/S, jpr@
T90(D86) or T90(D2887) or T95(D86) in finished diesel fuels, topsoe.dk: Having industrial experience in producing ultra-
and how this translates into an operative value for T90(TBP) low aromatic diesel such as Swedish city diesel, dating back to
or T95(TBP) for heavy diesel gas oil per computer simulation the early 1990s, we have spent considerable time and effort
modelling. The latter may require the evaluation of relative on understanding catalyst effectiveness in relation to
contributions of light coker gas oil, FCC LCO, SR kerosene, optimised process design. This continuous effort has resulted
hydrocracked heavy diesel blendstock, and heavy diesel gas in an improved HDS/HDA technology being a cost-effective
oil to 608–662ºF and 662ºF Simdist fractions in typical solution for upgrading heavy diesel fractions to high-quality
finished ULSD fuels. For new crude/vacuum distillation units, ultra-low sulphur diesel. The development in dearomatisation
the following options are then explored via parametric catalyst has resulted in the commercialisation of catalysts
computer simulation modelling to maximise the volume with four times higher activity for the saturation of aromatics.
percentage or barrels per stream day (BPSD) output of heavy The result is that the required catalyst volumes have been
straight-run diesel gas oil within the operative constraint for reduced to a level that makes counter-current reactors non-
T90(TBP) or T95(TBP) determined previously: justifiable from an economical perspective.

www.eptq.com PTQ Q1 2009 23

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 FCC reactor design:
part II
In part I, reaction kinetics, cracking chemistry, pressure balance, catalyst and vapour
residence times, and fluidisation were considered. In part II, feed injection technology
and riser termination devices to minimise dilute-phase cracking are reviewed

Warren Letzsch, Chris Santner and Steve Tragesser

Shaw Energy & Chemicals Group

T
he feed injection system is the ratio of 5.0 and a catalyst particle size of catalytic cracking can be classified as
most important aspect of any 70 microns into Equation 3, a single oil either of two fluid nozzles: oil and steam
fluid cracking process, since droplet of 280 microns must contact or pressure nozzles. Pressure nozzles
this is where the feedstock is brought 199 catalyst particles, while a 70 micron atomise by applying pressure to a liquid
into contact with the hot catalyst. In oil droplet (the same size as the catalyst and then forcing it through an orifice.
addition to vapourising the feed so particles) would contact about three Today, all of the commercially available
catalytic cracking can proceed, the entire particles. It is highly unlikely a single feed nozzles offered by FCC licensors are
feed injection system must perform droplet can contact about 200 catalyst of the two fluid nozzle type. Nukiyama
other essential functions, including particles. As a consequence of these and Tanasawa found the following
quenching the hot catalyst coming from hydrodynamics, the larger droplets will correlation for two fluid nozzles:
the regenerator as quickly as possible not be able to directly quench all of the
1920 σ 0.5 µ 0.45 L ρg 1.5 (4)
and contacting all of the feed with catalyst particles. This results in a higher Dsm = d n + 597 d , n d1000 n
U ρ, :σρ, G ρl
the catalyst. average reactor temperature, a higher
Since vapourisation of the feed is delta coke and more dry gas in the case Where:
essential to the process, small oil droplets of large oil droplets. Dsm = Sauter mean diameter, microns
must be produced to ensure rapid heat A large amount of heat transfer must σ = surface tension liquid, dynes/cm
transfer. This is illustrated by the take place between the catalyst and oil. ρ,, ρg = liquid and gas density, gm/cm3
following analysis. If oil droplets and The smaller droplets have four times the µ, = viscosity liquid, poise
catalyst particles are assumed to be external surface area in the previously U = relative velocity of gas and liquid
spheres of diameter Do and Dc respectively, mentioned case. The higher heat transfer L/G = liquid/gas mass ratio.
the weight of the catalyst and oil in the rate and the smaller diameter drops This equation has two terms that
riser is: greatly increase the rate of vapourisation contain both the fluid properties and
of the oil. Table 1 by Mauleon shows the nozzle parameters. The second term
π
wt of catalyst Nc • Dc3 • ρc (1) value of a small oil droplet size for suggests the droplets will be smaller if
6
intimate catalyst/oil contacting and more gas is used relative to the liquid
rapid vapourisation. rate, while the first term relates to how
π
wt of oil No • Do3 • ρo (2) Buchanan’s analysis gave similar the two streams are brought into contact
6
results. He also found that heat transfer with each other. Higher relative velocities
where Nc, No are the number of catalyst between the catalyst and gas was almost create more shear and smaller droplet
and oil particles and ρc, ρo are the instantaneous, that heat transfer by sizes. When resid is processed, the
densities of the catalyst and oil particles. radiation is much slower than for droplet sizes tend to increase due to
The catalyst-to-oil ratio is simply (1) convection and that the droplet increases in the surface tension and
divided by (2) or: temperature will be equal to the wet- viscosity of the oil. The modified Mogele
bulb temperature based on the surface equation shows this relationship:
Nc * Dc3 * ρc (3) composition. The number of large
CAT/OIL =
No * Do3 * ρo droplets is important, since a few of Dresid σresid 0.5 µresid 0.2 ρvgo 0.3
=d n d n d n
these may comprise a relatively large Dgasoil σgasoil µvgo ρresid (5)
Substituting for the densities (56 and percentage of the feed on a weight
90 lb/ft3 for the oil and catalyst basis. Typical numbers for gas oil and resid
respectively), assuming a catalyst-to-oil All of the feed nozzles used in fluid suggest resid would produce droplets
about twice the size of gas oil feeds.
Correlations of each of these fluid
Feed atomisation (feed nozzle exit velocity: 50 m/s) properties vs temperature show each
increases significantly as the feed
Oil droplets size, microns 500 100 30 temperature is reduced from 700–350°F.
Relative number of droplets 1 125 4630 The changes are largest below 450°F.
Catalyst particles per oil droplet 1000 9.09 0.25 Other nozzle features that play a role
Vapourisation time, m/s
in feed/catalyst contact are the spray
At 50% /= vapourisation 220 11 4
angle, evenness of the spray (uniform
At 90% /= vapourisation 400 20 8
flow rate) and penetration into the
centre of the riser. These features
Table 1 control the overall distribution of the

www.eptq.com PTQ Q1 2009 25

 revamp. The reduction in dry gas and
delta coke frees the unit of gas and coke
limits, and the increase in gasoline of
Regenerated catalyst temperature 6.2 vol% is quite valuable. Research
octane number may drop by 0.5–1.0 due
to the lower average reactor temperatures,
even though the riser outlet temperature
is unchanged. However, this effect can
Cat. temperature

be minimised by a change in operating

Poor conditions and catalyst.
Thermal cracking
and coking region The pressure balance around the feed
Fair injection system at the base of the riser
is also important. A typical riser layout is
Good shown in Figure 2 with four pressure
Riser outlet temperature locations. Point 1 is the pressure at the
outlet of the regenerated catalyst slide
valve, which equals the pressure at point
Feed injectors Riser length
4, the riser base. Typically, no static head
build-up is assumed from the outlet of
the slide valve to the bottom of the riser.
Figure 1 Influence of feed injector design on FCC reactor yields Point 2 is located at the feed injection
point, and point 3 is at the riser outlet.
When a modern, radial feed system
FCC feed nozzle effect replaces an axial system, the overall
Axial Advanced radial Delta pressure drop across the slide valve
Feed rate Base 1.04 Base typically drops by 0.5–1.0 psi, since the
Dry gas (FOE vol%) 4.44 3.1 1.34 pressure drop from the slide valve to the
LPG, vol% 25.51 27.05 15.54 feed nozzles increases more than the
Gasoline, vol% 55.11 61.27 6.16 decrease in riser pressure drop due to
LCO, vol% 22.23 17.75 -4.48 more even contacting.
Slurry, vol% 4.23 3.94 -0.29 Feed nozzles are typically located as
Coke, wt% 5.18 5.12 -0.06 low as possible in the riser to maximise
Conversion, vol% 73.5 78.3 4.8 the slide valve pressure differential.
C3+ liquid, vol% 107.1 110 2.9 Raising the feed nozzles above this
Feed preheat, °F 459 472 13 decreases the active riser length and
Riser temp, °F 1000 995 -5 greatly reduces the slide valve pressure
Regenerator temp, °F 1323 1270 -53 drop. For example, if the nozzles are
C/O ratio 6.4 7.4 1 located 30ft downstream of the riser, the
Delta coke, wt% 0.81 0.69 -0.12 total loss of pressure would be about
5.0 psi, assuming a catalyst density of
Table 2 25lb per cubic foot. The only way to
minimise this pressure loss is to add
feed across the riser cross-section in This is illustrated in Figure 1. steam or lift gas to the bottom of the
the feed injection zone. If everything The improvement in yields can be riser, which can reduce the catalyst
is done properly, the temperature in quite significant, with payouts of three density to 10–15lb per cubic foot. The
the riser should drop quickly and months or less for revamps to existing table in Figure 2 illustrates this point.
catalytic cracking will be maximised, systems. As an example of this, Table 2 However, using lift steam has a
and thermal reactions will be suppressed. gives the before and after yields for one detrimental effect on the main
fractionator and overhead condenser.
The use of lift gas also increases the load
on the wet gas compressor.
Two positive features cited by some
2ISER 4EE
for lift gas is the lower density at the

point of feed injection, allowing greater
R2 feed penetration and the passivation of
.OTE 0 z 0 contaminant metals that accumulate on
L 0 n 0 z R2" H the catalyst when processing heavier
0 n 0 z R2 L ACCEL feeds. This passivation occurs when off-
Catalyst $P/10 feet gas from the process is recycled to the
density base of the riser. However, sufficient
 10 0.70 time is necessary to change the oxidation
15 1.04 state of the metals before the feed is
R2" 20 1.39 introduced. Testing has shown that a
25 1.73
H
30 2.08
length of 70–80ft is required to have any

passivation benefit, while a short
 distance of 10–12ft showed no positive
effect. Steam was originally used as the
lift medium, but catalyst deactivation
occurred due to the metals levels on the
catalyst and the temperature of the
Figure 2 Typical riser layout catalyst coming from the regenerator.

26 PTQ Q1 2009 www.eptq.com

Steam was preferred, since it could be
condensed and recovered in the
overhead accumulator. However, dry gas 
had to be substituted to prevent the loss
of catalyst activity. Contaminant metals d(C2–)wt% = Kt
on catalysts can be passivated with feed K = 8.3E12 exp [–93000/1.987/T(R)]

additives such as antimony or bismuth.
Gamma scans have been done on
commercial catalytic crackers with

diameters of 72in (6.0ft). Modern feed
nozzles with velocities of over 200 ft/sec, 20 s

$RY GAS WT

penetrated the middle of the riser
without a significant amount of lift gas. 
The density in the riser changes abruptly
at the point of feed injection, which 10 s
may assist with feed penetration, since 
the feed is not injected as a flat spray,
but rather as a wedge of droplets. 5s
The final and possibly most important 
consideration for the feed injection
system is its mechanical reliability. If the 1s
feed nozzle erodes or fails during a run, 
the loss of yield performance can have a        
significant economic impact on the 4EMP #
profitability of the unit. If feed nozzle
steam is lost, catalyst will aspirate back
into the feed nozzles, which can lead to Figure 3 Dry gas production vs temperature and time
plugging and erosion of the nozzle.
Also, feed nozzles with small orifices will
tend to plug and may not completely
clear when steam is regained. Scale from
pipes and solids in the feed can also plug
small orifices on either the steam or feed
side. Feed nozzle tip erosion can be a
major problem. If the tip is completely
lost, feed distribution and atomisation
will be severely impacted. Also, coverage
of the riser cross-section may be reduced
from almost 90% of the cross-sectional
area to about 30%, resulting in a loss of
20–50 cents per barrel of feed processed.
In resid operations, coking may become Exxon Texaco/Lummus
severe, resulting in unplanned and
costly shutdowns.
Careful design of the entire feed
system is required to ensure good
performance and mechanical reliability
of the feed nozzles. This can include
precision machining of the nozzle and
hard surfacing of the feed nozzle tip to
ensure integrity during operation. A
properly designed feed injection system
should not suffer serious damage to the
feed nozzle over an entire four- to five-
year run length.

Riser termination Mobil/Kellogg

advancements
Riser termination technology has UOP
become a necessity with modern reaction
systems. The high activity catalysts have
essentially made riser cracking the entire Figure 4 Closed-coupled configurations for catalyst/vapour separation
reactor, and significant non-selective -A
cracking was found to occur at the Dry gas production (SCF) = Ke /RT
(time) (6) The value for the activation energy
typical riser outlet temperatures obtained from the commercial data
employed today (520–550°C/968– A = Activation energy; 93 000 Btu/lb- agreed well with the laboratory value. A
1022°F) in the dilute phase of the mole small number of hydrogen transfer
reactor-stripper vessel. Amoco did K = Rate constant; SCF/Bbl-sec reactions probably accounts for the
extensive work on commercial crackers R = Gas constant difference. Figure 3 is a plot of the
and found an Arrhenius-type T = Dilute phase Rx temp; °R Amoco correlation. At low reactor
relationship, where: Time = seconds. temperatures, the amount of dry gas

www.eptq.com PTQ Q1 2009 27

produced in the dilute phase is small. will also prevent the secondary cracking (negative-pressure cyclone) the dipleg
Higher temperatures and long reaction reactions in the dilute phase. This is level is above the reactor-bed level. As
times cause very high dry gas yields. accomplished by essentially connecting long as both positive- and negative-
The vapour quench technology the primary and secondary catalyst- pressure cyclone diplegs are adequately
reduces the dry gas make by lowering vapour separation devices in the reactor. sealed and the catalyst density in the
the dilute-phase temperature. This is The primary separation device should be diplegs is the same, the amount of
illustrated in Figure 3 by moving to the fixed to the end of the feed riser. All vapour carried under with the catalyst
left down the appropriate residence time current licensors of FCC technology offer will be the same. This was demonstrated
curve. The keys to successful quench a close-coupled riser termination system. by Mott, who showed that the volume
operations are the effective separation of The catalyst/vapour separation in the of the catalyst travelling down the
the spent catalyst from the riser outlet primary separator must be very high; diplegs of the primary separator is
vapours prior to quenching, the use of a otherwise, the reaction products are essentially Vgas. This is calculated from
refractory quench material that will not contacted with hot, spent catalyst for an Equations 7 and 8:
crack or coke, controlling the temperature extended period of time, promoting non-
so that condensation of liquid does not selective cracking and higher delta coke. Ve = 1000 Qcat/ρε (7)
occur and safeguards to ensure the Vapour containment is a secondary
quench medium is removed consideration related to the amount of where
automatically in the event of certain underflow from the primary separator. Ve = volume catalyst emulsion, m3/
unit conditions. These may include the Even three or four seconds of contact of min
loss of feed, when minimum reactor the reaction products with spent catalyst Qcat = catalyst circulation, mt/min
temperature is encountered or the loss will produce a lot of dry gas due to the ρε = fluidised standpipe (dipleg)
of power to the unit. high surface area presented by the catalyst density, kg/m3.
Vapour quench has the advantage and its high heat capacity that keeps the The total volume of interstitial and
that it can be turned down or off. When cracking temperature from dropping. intraparticle gas circulated with the
fuel gas has a very high value or the In Figure 4, three closed-coupled catalyst is:
refinery is short on fuel gas, it might be configurations are shown. These differ
desirable to discontinue the use of according to the location of the vent, ρε (8)
Vgas = Vε d1 – d nn
quench. This is not possible with a short which allows the stripper vapours to ρskel
contact time riser termination device. enter the cyclone system for recovery. If
The initial quench medium has the the vapour entry space is before the where
largest impact on reducing dry gas, since primary cyclone, the primary cyclone Vgas = volume gas carried with catalyst
it is applied to the highest temperature. becomes a negative-pressure cyclone. ρskel = skeletal density of catalyst.
Another benefit of lowering the Clearly, the pressure in the dilute phase Since the catalyst flow through the
dilute-phase thermal cracking is the must be greater than the pressure in the primary cyclones is the same for either
reduction in diolefins. This includes the primary cyclone when the system is cyclone system and essentially equal to
butadienes in the LPG stream and the sealed or the gas could not leave the the catalyst circulation rate, the
pentadienes in the gasoline. Butadienes reactor vessel. underflow would be identical.
are known to increase acid consumption When the stripper vapours enter The size of the dipleg will influence
and to produce more acid soluble oils between the first- and second-stage the amount of gas underflow from the
(ASOs) in alkylation units. Less desirable cyclones, the pressure in the dilute phase separator. Normal designs have flux rates
side reactions will occur as well, resulting is less than the pressure in the primary that result in a catalyst velocity of at
in a higher alkylate end point. Gasoline cyclone. Hence, the primary cyclone has least 3.0 ft/sec downward that does not
diolefins lead to poorer stability in a positive pressure. allow any gas to separate from the
storage and require more chemicals to These differences are reflected in the catalyst. The catalyst separation may be
prevent colour bodies and gum operation of the diplegs. In the latter slightly higher under this scenario and
formation. case, the catalyst level is close to the has been a primary design consideration
Reducing the vapour residence time reactor-bed level, while in the former for catalyst/vapour separations, since
this minimises catalyst carryover to the
main fractionator. Normal dipleg fluxes
are 80–120 lb/ft2-sec. If the flux rate is
Anti coking
ring Window below 40 lb/ft2-sec, the gas bubbles may
connecting rise in the dipleg and leave through the
separation and
stripping gas outlet tube. This will create a higher
chambers density in the standpipe and minimise
Slip fit for vapour underflow. Excessive underflow
expansion leads to higher dry gas make, higher
Separation delta coke, higher regenerator
Stripping
chamber chamber temperatures and lower than desired
Dipleg
catalyst circulation rates.
Opening for
Pre- stripper gas Other variations of the basic two-
stripping cyclone system have been utilised.
Stripping
Main internals Petrobras removed the primary dipleg to
stripping Riser prevent plugging with coke that may
ring
form during resid operations. While all
Stripping
chamber of the gas leaves through the primary
Separation Stripping cyclone, the underflow is significant,
compartments compartments
since the catalyst will drag gas along
with it as it leaves the primary cyclone.
A vortex separator is a closed system
Figure 5 Axial cyclone type reactor separator-stripper coupled to conventional that has one large primary separator
secondary cyclone system sealed in the stripper. All of the stripper

28 PTQ Q1 2009 www.eptq.com

 catalytic cracking risers, Ind. Eng. Chem.
Riser terminator improvements Res, 1994, 330, 3104–3111.
3 Mauleon J-L, Total Petroleum N.A., Private
Feature Effect Communication.
Separation eff. (solids/gas) Essential to stopping secondary reactions 4 Legendre M, Total Petroleum N.A., Private
Communication
Separator volume Minimise to reduce secondary reactions 5 Perry-Chemical Engineer’s Handbook, Fifth
Edition, McGraw Hill, 18–58 to 18–67.
Underflow of gas Minimise to reduce dry gas and delta coke 6 Gauthier T, Gius D, IFP internal report.
Dipleg flux Determines gas entrainment with catalyst 7 Upson L L, Kruff D A, Lacijan L A, FCC
reactor technology developments, NPRA
Annual Meeting.
Location of stripper gas Residence time of underflow and stripper gases 8 US Patent 5 306 418.
inlet to separator 9 Anderson S, et al, Feed injection system
Operate sealed or unsealed Versatility to optimise yields replacement project, NPRA Annual
Meeting, AM-97-09.
10 Challis S, Chen A, Davuluri R, Tailor-
Dilute-phase stripping Minimise delta coke made RDD feed zones, Grace Technology
Resistance to upsets Avoid unscheduled shutdowns and higher maintenance costs Conference, Rome, Sept 2007.
11 Letzsch W S, O’Reilly W, The design and
installation of FCC feed injection systems.
Table 3 12 Driskill B S, Reeves J L, Silverman M R,
Quinn G P, Post-riser quench technology
vapours pass up through the primary While reactor design can be broken paper, Stone & Webster Second FCC
Forum, Woodlands, Texas, 1996.
separator and leave through the outlet down into individual components, the 13 Letzsch W S, Controlling FCCU dilute
tube. Vapour is kept within the system, entire system should be analysed and as phase reactions, PTQ, Q2 2005, 49–53.
but catalyst separation in the primary many of the desirable features of the 14 US Patent 5 087 427.
15 Mott R W, Troubleshooting FCC standpipe
separator will be relatively low. feed injection system, reactor flow problems, Davison Catalagram.
The reactor separator-stripper shown configuration and the termination
in Figure 5 is an axial cyclone coupled to system should be employed to meet the
a conventional secondary cyclone current and future requirements of the
system. The stripper vapours pass job. And, as a final point, the stripper Warren Letzsch is Senior Refining
through the stripper chambers and into must be compatible with the new Consultant, Shaw Energy & Chemicals
the secondary cyclones. Catalyst operating regime; otherwise, many of Group. Email: w.letzsch@shawgrp.com
separation in the primary separator is the projected benefits will be lost. This Chris Santner is Manager, Catalytic
slightly lower than a cyclone due to the will be discussed in a future article. Cracking Technology, Shaw Energy &
reduced number of turns, but the system Chemicals Group.
works at any velocity unlike a cyclone References Email: c.santner@shawgrp.com
and does not require additional steam 1 Mauleon J-L, Courcelle J C, Oil & Gas Steve Tragesser is FCC Technology
Journal, 21 Oct 1985, 64–70.
usage in the riser to achieve a minimum 2 Buchanan J S, Analysis of heating and Manager, Shaw Energy & Chemicals
inlet velocity for the primary separator. vaporization of feed droplets in fluidized Group. Email: s.tragesser@shawgrp.com
It also has large diplegs, which makes
the separator very robust, thereby
minimising the risk of catalyst carryover ★

to the main fractionator during unit

upsets. All of the two-stage riser
separators achieve high overall catalyst 3rd
separation and, in normal operations,

refining
catalyst carryover to the main
fractionator is low.
Riser terminators have undergone
continuous improvements over the

China
years, as both licensors and users have ★

★
acquired additional information on
their performance and design. In ★
addition, changes in catalyst formulation,

2009
operating conditions and feedstock ★
components contribute to this evolution
of knowledge. While eliminating dilute- ★
phase cracking and increasing gasoline
yield was the first objective, many more

17–18 March 2009

considerations have come to light. These
are listed in Table 3.
For new units, a modern riser
termination system is easy to install. For
revamps, the best solution will depend
on the current equipment used and how
Beijing
the unit is configured. Factors such as
vapour residence time and the desired The networking event of the year for everyone
reactor temperatures are important, as with an interest in refining technology in China.
are gas plant limitations. Frequently, a
solution that might give 90% of the Combine it with a visit to CIPPE, 19-21 March
benefits is better than one that costs
millions of dollars more to install and
gives only marginal additional
www.refiningchina.com
advantages.

www.eptq.com PTQ Q1 2009 29

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 Stabilisation
of asphaltenes
Asphaltenes can plug refinery equipment and can decrease or stop production.
Stabilisation of asphaltene particles is an efficient and cost-effective way to avoid
undesired asphaltene agglomeration or precipitation

Berthold Otzisk and Hermann Kempen

Kurita Europe

F
rom the oil well through the fouling material, similar to that shown of the pendant groups results in a lower
refinery, fouling can interfere in Figure 1, is often transported from the solubility of the asphaltenes. The
with production equipment. It is well tubing to the flow lines, separator, asphaltene free radicals combine to form
a common problem for oil production process pumps, strainers and other high molecular weight and insoluble
companies and refiners, and periodically downstream equipment. Asphaltenes coke.
process units have to be shut down for are sensitive to shearing forces and Crude oils are a mixture of many
mechanical cleaning due to fouling, electrostatic interactions, and crude organic compounds, and their overall
resulting in throughput losses or distillation and vacuum units often are properties differ from well to well.
production shutdown. The incentives to affected by asphaltene fouling. Crude Residual oils from the Middle East and
reduce fouling are therefore significant, preheat train and vacuum bottom heat Latin America are often rich in
such as increased productivity and exchangers can plug, and as a result asphaltenes. A high asphaltene content
reduced operational costs. require chemical or mechanical cleaning; means a high Conradson carbon residue
The fouling phases can be coke, otherwise, throughput has to be reduced, (CCR) and a high metals content (nickel
asphaltenes, wax, stable emulsions or leading to a loss of production. and vanadium). CCR is the amount of
inorganic solids. Refiners are currently FCCUs often report fouling problems coke produced in a standard thermal
converting more residuals into light in the slurry circulation system. cracking test, and is a measure for
fractions, which results in heavy fuels Asphaltenes, catalyst slurry fines, coke potential coke formation at high
production that contains a higher particles and dehydrogenated temperatures.
concentration of asphaltenes. Most polynuclear aromatics (PNAs) can all
organic fouling is caused by insoluble cause fouling. Analytical methods
asphaltenes, including coke formation. The best strategy for reducing fouling It is essential for a refiner to know the
Asphaltenes are components of is to use basic knowledge to eliminate its asphaltene concentration in crude oil,
petroleum, and their behaviour and formation. Asphaltenes do not melt residue or heavy fuel. There are a
structure change with temperature, above 300–400°C; instead, they number of analytical instruments and
pressure and the composition of oil. decompose, forming carbon and volatile methods on the market to analyse the
Unwanted asphaltene precipitation can components. Asphaltenes contain structure of asphaltenes, including:
plug well bores and distillation thermally stable PNA cores, and their — X-ray analysis
equipment and, in many cases, decrease pendant groups are connected to the — NMR spectroscopy
or stop production. core by thermally unstable bonds. These — Mass spectral methods
Asphaltenes and resins are responsible bonds break to form free radicals above — Elemental analysis
for adding most of the colour to crude 350°C. The dispersed asphaltenes — Diffusion techniques.
oils. Asphaltene particles have a high abstract hydrogen from hydro-aromatics The main diffusion techniques are:
affinity to associate with one another and terminate the free radicals. The loss — Fluorescence correlation spectroscopy
and a high tendency to adsorb resins. (FCS)
The wide range of size distribution — Time-resolved fluorescence
indicates that asphaltenes are partly depolarisation (TRFD)
dissolved and partly in a colloidal and/ — Taylor dispersion.
or micellar form. Resins are not known Asphaltenes are very complex
to precipitate on their own, but they do molecules. Their structure is often
deposit with asphaltenes. At a low desorbed to a compact stack of many
temperature, waxy crudes containing thin sheet-like layers (similar to that of a
small amounts of asphaltenes can book). They are suspended by tiny
behave differently to a clean, waxy colloidal particles in crude oils. The
crude containing no other heavy molecules are stabilised by natural resins
organics. and maintained in the oil due to its
Asphaltene precipitation during oil stabilisation.
production and processing is a serious The industry’s knowledge of
problem. The economic implications are asphaltenes is still limited and little is
significant and can cost millions of known about their chemical properties.
euros. In some cases, fouling problems Asphaltenes are lyophilic with respect to
have been reported to be so drastic that aromatics, in which they form colloidal
many oil wells have been redrilled. The Figure 1 Asphaltene precipitation solutions. Removal of the small colloidal

www.eptq.com PTQ Q1 2009 31

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particles or resins immediately results in indication of the separability number
instability of the oil. The consequence is and flocculation tendency:
the formation of an agglomeration, — High stability reserve = no
followed by precipitation. flocculation
ASTM D2007-80 is a widely recognised — Medium stability reserve =
standard procedure for separating flocculation if oil exposed to worse
asphaltenes from crude oils. The solvent conditions
n-pentane is used for asphaltene — Low stability reserve = easy
precipitation, followed by filtration. The flocculation.
filtered asphaltenes must be dried under The measuring technique is based on
a hood for several days. If the drying the principle of multiple light scattering.
process is too slow, the asphaltenes can The intensity of the backscattered light Your global partner for
be redissolved in a minimal amount of is in direct correlation to the moisture, hydrocarbon
toluene. They can then be reprecipitated concentration and average diameter of
with an alkane of lower molecular the dispersed phase (particle, droplet dew point and gas
weight and a higher volatility. The dried
filtered asphaltenes can be weighted to
and bubble). The instrument has a
pulsed infrared source (850 nm) and two
analysis
determine the amount of asphaltenes in synchron working detector systems:
the oil. — Transmission detector
characterisation of clear products
for
• Gas production
Alkane titration — Backscatter detector for • Fiscal metering
Operationally, asphaltenes are defined
to be insoluble in alkanes like n-heptane
characterisation of opac concentrated
products.
• Natural gas storage
and soluble in aromatic solvents like In vertical direction to the sample • Refinery recycle gas
toluene. ASTM D7157 is a standard test container, the transmission and • LNG facilities
method for determining the instability backscattering data are taken every 40
of asphaltene-containing residues, µm (up to a maximum height of 80 • Power generation
heavy fuels and crude oils. There are a mm). According to the program, the plants
number of suitable automated fuel scanning is designed to give a report
stability analysers on the market that with multiscans. Any changes in the
conform to ASTM D7157. stability of the sample are detected,
The operating principle is based on an which gives an indication of the
alkane titration and optical detection of destabilisation process. ASTM D7061-04
the precipitated asphaltenes. A sample describes the analysis in three main
dissolved in toluene is titrated at room steps, which are:
temperature with n-heptane. The optical — Dilution of heavy fuel oil (HFO) in
probe monitors the formation of toluene
flocculated asphaltenes during the — Precipitation of asphaltenes with
titration. Within 15–30 minutes the test n-heptane
result can be achieved. Depending on — Measure stability using the
the optical probe system, some Turbiscan.
automated instruments are limited to The Turbiscan instrument is useful for
products containing a minimum of determining the best antifoulant or
0.5% asphaltenes. stabilisation additive at the optimal
concentration. It is a standard Kurita
Heavy fuel instrument procedure to optimise the dosing rate of
One accurate method uses Turbiscan asphaltene dispersants by using
technology and conforms to ASTM Turbiscan technology. The difference
D7061-04. It measures the stability between an unstabilised or stabilised
reserve of heavy fuel oils upon ageing sample can be detected quickly with
simulation (precipitation of asphaltenes high accuracy.
in alkane). Typical applications are the
control of heavy fuel oils, residues, Stabilising the asphaltenes
compatibility of blends and the effect of Historically, the fraction insoluble in
additives. The Turbiscan MA 2000 Heavy n-heptane has been called asphaltenes.
Fuel instrument is a special development Using modern analytical techniques,
of the Turbiscan MA 2000 and combines the complex structure of asphaltenes Precision made easy
several benefits, including can be analysed more deeply. In general,
— Flexible instrument the macrostructure of asphaltenes is
— Easy technique composed of several sheet-like layers of
— Quick analysis condensed polycyclic aromatic
Michell Instruments Limited
— Quantitative and qualitative compounds with porphyrin-like
48 Lancaster Way Business Park
analysis. structures.
Ely
The instrument enables the accelerated In 1967, the macrostructure of
Cambridgeshire CB6 3NW
detection of stabilisation tests and their asphaltenes was well described by Dickie
United Kingdom
documentation. By vertically scanning and Yen to be a composition of these 13
T: 01353 658000
the sample container (Turbiscan cell), items:
asphaltene stability can be determined. — Crystallite and particle
The instrument detects destabilisation — Chain bundle and single layer www.michell.com
phenomena 4–50 times earlier than the — Micelle and resin
naked eye. The automatic result gives an — Weak link, gap and hole

www.ptqenquiry.com
www.eptq.com for further information PTQ Q1 2009 33
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— Intra- and interstructure
— Petrophyrin and metal.
Asphaltenes are believed to exist 18
partly dissolved in oil and partly in a
colloidal and /or micellar form. Small 16
asphaltene particles can be dissolved in
oil by using expensive aromatic washes. 14
Relatively large asphaltene particles can 12
flocculate and form steric colloids in the

Delta transmission, %
presence of excess amounts of resins and 10
paraffin hydrocarbons. These asphaltenes
are highly polar surface active 8
compounds. Destabilised asphaltenes 6
act as glue and mortar in hardening the
deposits. The flocculation of asphaltenes 4
in paraffinic crude oils is known to be
irreversible. 2
It is better to avoid destabilisation of
0
asphaltenes. Based on experimental
evidence, there is a critical resin –2
concentration below which the
asphaltenes precipitate. Above the
0 20 40 60
critical resin concentration, they cannot mm
precipitate regardless of how much the
oil mixture is heated, agitated or
pressurised. Several investigators Figure 2 Untreated vacuum bottom sample
measured the critical micelle
concentration for solutions of asphaltene
in aromatic solvents. Below the critical
micelle concentration, the asphaltenes
in solution are in a molecular state. 10
Above the critical micelle concentration,
the formation occurs in a manner similar
8
to that in surfactant systems. These
monomers are less poly-dispersed and
much more uniform in their structure.
Delta transmission, %

6
In the presence of excess amounts of
hydrocarbons, the asphaltene may self-
associate, but not flocculate and form 4
micelles. The mechanisms of asphaltene
flocculation and steric colloid formation
are well understood. The theories of 2
micellar solutions of oil, surfactant or
water are well known, but the phase 0
behaviour of asphaltene micelle
formation is not well characterised.
Kurita’s asphaltene dispersants are –2
substitutes for the natural resins. They
work by surrounding the asphaltene 0 20 40 60
molecules, similar to the natural resins. mm
The critical resin concentration is shifted
to a higher level, resulting in a more
stabilised asphaltene solution. This Figure 3 Stabilised vacuum bottom sample
keeps the hydrocarbons in a colloidal
system and the asphaltenes in a disperse stabilised vacuum bottom sample with a Case study
phase to prevent fouling and plugging. low tendency for asphaltene In 2000, a Western European refinery
Figure 2 shows the multiscan of an precipitation. The vacuum bottom revamped its FCCU and later noticed
untreated vacuum bottom sample, taken sample was treated with 20 ppm of a an increased fouling in the slurry oil
by a Turbiscan MA 2000 Heavy Fuel. suitable antifoulant programme. The exchangers. Several service companies
Over 15 minutes, one scan was recorded asphaltene stability is a function of the tried to solve the problem by dosing
per minute. The wide range between the dosing rate. A higher dosing rate of their chemical programmes, but the
first and the last scan is an indication of approximately 30 ppm will give a higher situation worsened and the financial
the instability of the vacuum bottle stability with virtually no difference losses for the unit climbed to
sample. The refinery unit where the between the first and last scan. Based on €1 400 000 per year.
vacuum bottle sample was taken is experience, the additive concentration The FCC slurry system is a network of
incurring severe asphaltene problems. required for lab tests is higher than the heat exchangers designed to remove
Without a successful antifoulant dosing rates needed for an operating heat from the cracked product. This
programme in place, the heat exchangers refinery application. Thermodynamics heat is used again to preheat the FCC
are having to be cleaned mechanically play a big role, which cannot be simulated feed to generate steam and fractionate
every six to eight weeks. with most laboratory procedures and and recover products downstream. The
Figure 3 shows the multiscan of the methods. cooled slurry oil is again returned to the

www.eptq.com PTQ Q1 2009 35

 stability and dispersing power, which
allows the refiner to optimise its heat
A & B steam generators recovery from the FCC main fractionator
30
bottom stream. A higher FCC reactor
28 Start outlet temperature under more stringent
treatment
26 conditions is possible.
After optimisation of the dosing, the
24
refiner noticed an improved heat
Days in Gc al/ h

22 removal, to cool the bottom of the main

20
fractionator and achieve optimal
fractions. The product recovery improved
18 and losses of C4 olefins were significantly
16 reduced. No throughput limitations and
reductions for cleaning and maintenance
14
costs were reported. After positive
12 evaluation of the test run, the refiner
10 decided to continue the treatment and
0 100 200 300 400 500 600 700 800 900 1000 1100 1200 AP-2103 D2 has been continuously
Days applied to date.

Conclusions
Figure 4 Duty calculation of the two steam generators Asphaltene precipitation is a common
problem for oil production companies
and refiners. The economic implications
A & B steam generators can be significant, resulting in
0.0040 throughput losses or production
Start shutdown.
treatment Current knowledge of asphaltenes
0.0035
and their chemical properties remains
Fo uling f ac t o r in [m 2 oC/ W]

limited. However, there are now a

0.0030 number of suitable analytical
instruments and methods on the market.
0.0025 It helps to get a better understanding
and indication of the asphaltene
concentration and fouling potential.
0.0020 Asphaltene particles have a high
tendency to adsorb resins, resulting in
0.0015 undesired asphaltene precipitation.
Powerful asphaltene dispersants are
0.0010
substitutes for the natural resins. By
0 100 200 300 400 500 600 700 800 900 1000 1100 1200 surrounding the asphaltene molecules,
Days they keep the asphaltenes in a dispersed
phase to prevent fouling and plugging.

Figure 5 Fouling factor calculation of the two steam generators

References
1 Dikie J P, Yen T F, Macrostructures of the
main fractionator, where it acts as a fouling as soon as possible. The FCCU asphaltic fractions by various instrumental
quench stream. Unit throughput has to was already in fouled conditions, making methods, Anal. Chem. 39, 1967.
be reduced if the heat cannot be removed it more difficult to obtain the best 2 Leontaritis K J, Mansoori G A, Asphaltene
deposition: a survey of field experiences
through exchange with other streams. performance. An initial survey was and research approaches, Journal of Pet. Sc.
Slurry circulation is integrated with the started in order to have a full and Eng, 1988.
FCC product recovery system, and poor understanding of the fouling problems 3 Becker J R, Crude Oil — Waxes, Emulsions
and Asphaltenes, PennWell Books, 1997.
product recovery will cause significant in the system. This involved an intensive 4 Takatsuka T, Inoue S, Hori Y, Role of
economic losses. The slurry circuit is data collection and information asphaltenes cracking in bottoms conversion,
commonly used to reboil the debutaniser exchange between the operator and PTQ, Spring 1999.
tower, which can lead to losses in C4 Kurita.
olefins and potentially cause the FCC A six-month trial was started after
gasoline to be off-spec on vapour determination of the exact follow-up Berthold Otzisk is Consulting Engineer,
pressure. procedures. The necessary analyses and technical department, at Kurita Europe,
Heat exchanger cleaning costs can be tests were defined and the dosing point Viersen, Germany, focusing on refinery
significant, especially if throughput for the chemical treatment programme and petrochemical applications. Otzisk
must be reduced during cleaning determined. The selected product, Kurita has more than 15 years’ experience
operations. Cleaning activities in hot AP-2103 D2, was dosed into the slurry in sales, service and research of new
service can also become a safety and oil circuit (Figures 4 and 5) and it technologies. Email: otzisk@kurita.de
reliability concern. controls the fouling caused by: Hermann Kempen is Technical Manager
With all these problems, the refinery — Deposition of asphaltenes at Kurita Europe, Viersen, Germany. He
was forced to either shut down the — Catalyst slurry fines has more than 12 years’ experience in
FCCU or start with another chemical — Coke particles R&D of water and process treatment.
programme. The current chemical — Dehydrogenated polynuclear Kermpen holds a PhD in chemistry from
antifoulant programme was terminated aromatics. Technical University of Aachen.
and Kurita was asked to reduce the Kurita AP-2103 D2 has a high thermal Email:kempen@kurita.de

36 PTQ Q1 2009 www.eptq.com

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 Maximising diesel
recovery from crude
The CDU/VDU process flow scheme is reviewed, including equipment design and
operating fundamentals used to maximise straight-run diesel recovery. Factors
important to increasing diesel yield are discussed in detail

Scott W Golden
Process Consulting Services Inc

I
ncreased recovery of straight-run flow scheme and atmospheric column
(SR) diesel from crude oil improves equipment design and operating changes
refinery profitability. Low crude/ Naphtha can improve recovery. However, diesel
vacuum unit (CDU/VDU) SR diesel recovery is limited by process and
recovery is caused by existing unit distillation fundamentals in the
Kerosene
Atmospheric

process flow schemes, equipment atmospheric column. It can be optimised,

column

designs and operating conditions. Since but it has fundamental limitations that
Diesel
many FCC or hydrocracker feeds contain constrain recovery. Only a few US and
25–35% or more diesel boiling-range AGO (FCC feed) many non-US refiners produce both
material, there is significant opportunity Crude oil atmospheric and vacuum diesel products
to improve recovery. Low or moderate (Figure 2). Fractionation is inherently
capital investments have increased better in a vacuum column, therefore
LVGO (FCC feed)
Vacuum

refinery ULSD product yields by more diesel recovery is greatly improved.

column

than 5% on whole crude. MVGO (FCC feed) Fractionation is driven by column

internal efficiency and the fractionation
HVGO (FCC feed)
CDU/VDU diesel recovery section’s liquid-to-vapour (L/V) ratio.
Refiners in the US have until recently The top section of the vacuum column
targeted maximum gasoline production Vacuum residue has a much higher L/V ratio than the
with little focus on CDU/VDU SR diesel atmospheric column, hence vacuum
recovery. Not surprisingly, few US columns fractionate better than
refiners achieve good SR diesel recovery. atmospheric columns no matter how
This is because most of the existing Figure 1 Atmospheric column diesel good the CDU design. Better fractionation
process flow schemes and equipment product — no diesel from vacuum column reduces the vacuum diesel product 95%
were not designed to maximise the SR to endpoint tail compared to atmospheric
diesel yield from crude, nor were the draws, and operate with very little reflux column diesel. Additionally, the
operating variables associated with these below the diesel product draw. combined atmospheric and vacuum
flow schemes optimised for maximum Furthermore, it is not unusual for a US diesel products have better cold flow
SR diesel recovery. Most US refiners refiner’s vacuum column feeds to contain properties due to improved fractionation.
produce SR diesel only from their 8–10% diesel, with only a few VDUs The CDU/VDU process flow scheme has
atmospheric crude columns. Even some producing a vacuum diesel product. It is the largest influence on SR diesel
of the new CDU/VDUs have not been also not unusual for a US refiner’s top recovery. The CDU/VDU must have a
designed for maximum recovery, because vacuum column side-draw product to vacuum diesel product draw to maximise
many major E&Cs (and some refiners) contain 70–90% 650°F (343°C) minus recovery.
continue to believe that diesel should be diesel boiling-range material. In most It is common for US refiners to
produced only from the atmospheric cases, this diesel ends up in the FCCU. produce an AGO product (Figure 1). This
column. Even though diesel margins are Refiners can quickly determine their stream is often combined with the
very strong, there are still many CDU/VDU performance by evaluating vacuum gas oil (VGO) products feeding
misunderstandings about maximising the amount of 650°F (343°C) minus an FCC or hydrocracker. Since
CDU/VDU diesel production. diesel material in the CDU/VDU streams atmospheric crude column fractionation
Many non-US refiners have designed feeding the FCC or hydrocracker. Even is inherently poor, AGO product contains
their CDU/VDU to maximise diesel though hydrocrackers may recover some 30–70% or more diesel boiling-range
recovery. Their atmospheric crude of this diesel boiling-range material, it material. To maximise diesel recovery,
columns have 10–14 trays between the may not be the most cost-effective place no AGO product should be produced or
flash zone and the diesel product draws. to process it. A well-designed CDU/VDU it should be fed into the upper section of
They do not produce an atmospheric gas produces FCC or hydrocracker feed the vacuum column (Figure 3), where it
oil (AGO) product as FCC or hydrocracker streams containing less than 5 vol% can be fractionated into vacuum diesel
feed. Moreover, the CDU/VDUs have diesel boiling-range material. and VGO products. Overall CDU/VDU
been designed or revamped to produce diesel product recovery and energy
diesel from the vacuum column’s top Process flow scheme consumption are improved when
side-draw. Conversely, many US refiners Most US refiners produce diesel product atmospheric column AGO is fed to the
have only two to five fractionating trays only from the atmospheric crude column vacuum column. The amount of diesel
between the diesel and AGO product (Figure 1). Changes to the CDU process in the AGO product will determine

www.eptq.com PTQ Q1 2009 39

 heavy crudes like Merey or BCF 17 must
balance atmospheric and vacuum column
distillate yields against VDU VGO product
Naphtha Naphtha
yield objectives. Atmospheric residues
from heavy crudes are so difficult to
Kerosene vapourise even with the best VDU design

Atmospheric
Kerosene
Atmospheric that atmospheric column distillate yields

column
column Diesel Diesel must be constrained. Increasing the
amount of diesel in the atmospheric
AGO (FCC feed)
Crude oil Crude oil AGO to vacuum residue increases the VGO product yield.
column Conversely, as atmospheric residue gets
Vacuum diesel heavier, VGO product decreases and
Vacuum diesel vacuum residue production increases.

Vacuum
column
Vacuum
column

Since maximising the VGO product yield

MVGO (FCC feed) MVGO (FCC feed)
increases the overall refinery liquid
HVGO (FCC feed) HVGO (FCC feed) volume yield and reduces coke
production, balancing atmospheric and
vacuum column diesel yields is
Vacuum residue Vacuum residue crucial when processing heavy and extra-
heavy crudes.

Atmospheric crude
Figure 2 Atmospheric and vacuum Figure 3 Atmospheric and vacuum fundamentals
column diesel products column diesel products with AGO feeding Understanding atmospheric and vacuum
the vacuum column column distillation fundamental
principles is crucial to optimising CDU/
VDU economics. The atmospheric
column internal reflux rate below the
diesel product draw and fractionation
efficiency determines the diesel yield
Diesel (Figure 4). The column design requires
Crude PA the correct number of trays or amount
oil of packing efficiency and it also needs
optimum internal reflux (L).
Fractionation efficiency alone will not
Internal Steam
reflux (L) produce maximum diesel product.
Diesel product Fractionation section L/V ratio is one of
the fundamental principles that
V
determines product yield. The vapour
AGO rate into the fractionation section is set
PA
by the vapour leaving the flash zone and
the column heat balance. In an
atmospheric column, the vapour rate
Steam (V) is large because it consists of overhead
product gas, naphtha, kerosene and
AGO product diesel product, in addition to the internal
Crude oil reflux. Internal reflux (L) is relatively
small because it consists only of overflash
and AGO product. Consequently, the
fractionation section L/V ratio is typically
Steam less than 0.1 on a molar basis.
Atmospheric column diesel and AGO
product fractionation are inherently
Atmospheric poor. All factors influencing the internal
residue reflux rate (L) should be considered
when revamping or designing a new
CDU to maximise the atmospheric
Figure 4 Atmospheric column internal reflux rate column diesel yield.
Fractionation efficiency depends on
incremental recovery from processing operating pressure and diesel product equipment design. Ideally, the diesel
AGO in the vacuum column. distillation. This energy can be used to fractionation section should have at
When revamping or designing a new preheat crude, whereas the same diesel least eight properly designed trays or a
CDU/VDU to improve diesel recovery, boiling-range material produced from packed bed with at least five theoretical
selecting the most economic process the vacuum column is withdrawn at stages of efficiency. Since atmospheric
flow scheme should also consider energy only 250–300°F (121–149°C), making it crude columns are typically large
efficiency and VGO product yield. impossible to cost-effectively recover the diameter, the fractionating sections are
Energy optimisation may set the proper heat. Balancing diesel production designed with two- or four-pass trays to
amounts of diesel from the atmospheric between the atmospheric and vacuum maintain a reasonable flow path length.
crude and vacuum columns. Atmospheric columns saves energy, especially with Tray chord lengths are long, while the
column diesel product is withdrawn at light and moderately heavy crude oils. tray liquid rate is low. Therefore, it is not
525–575°F (273–302°C), depending on Refiners processing heavy and extra- unusual to have poor tray efficiency in

40 PTQ Q1 2009 www.eptq.com

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the diesel/AGO fractionation section
due to very low weir loadings. Since the
internal reflux (L) decreases from the
tray directly below the diesel product
draw to the bottom fractionating tray, it
is critical to reduce the weir length $IESEL
0!
(picket fencing) based on the minimum #RUDE
liquid rate. Maintaining weir loading of OIL
approximately 2 gpm/in of the weir on
the bottom fractionation tray maintains /PTIMISE 3TEAM
tray efficiency at its intrinsic limit of REFLUX ,
approximately 60%. If weir loading $IESEL PRODUCT
drops below 1 gpm/in of the weir tray,
efficiency drops quickly. When using !'/
packing, good distribution of the 0!
internal reflux (L) and adequate vapour /PTIMISE
!'/
distribution at the bottom of the 0!
fractionation section are key to
maintaining efficiency. Proper 3TEAM
equipment design can materially !'/ PRODUCT
improve diesel yield or quality for a
#RUDE OIL
given internal reflux (L).
The atmospheric column diesel
product yield depends on the internal
reflux rate once a column is built. The
internal reflux rate (L) is controlled by 3TEAM
several variables, including the heater
outlet temperature, column operating
!TMOSPHERIC
pressure, pumparound heat removal RESIDUE
location, stripping section efficiency and
stripping steam rate. Raising the heater
outlet temperature or reducing the
column operating pressure increases the
amount of vapour generated in the flash Figure 5 Optimising atmospheric column heat balance
zone. This allows a higher internal reflux
when the column heat balance is
properly controlled. Improved stripping
section performance either through
higher efficiency or a higher stripping
steam rate also increases the amount of $IESEL
flash zone vapour, permitting higher 0!
#RUDE
internal reflux in the diesel fractionating OIL
section. For a given flash zone vapour
rate, the diesel fractionating section’s
internal reflux is determined by /PTIMISE 3TEAM
REFLUX ,
heat balance. $IESEL PRODUCT
Controlling column heat balance is
essential to maintain an optimum
internal reflux rate. Figure 5 shows a !'/
column with an AGO pumparound 0!
/PTIMISE
located below the diesel fractionation !'/
section. AGO PAs are used because the 0!
pumparound draw temperature is 50–
3TEAM
100°F (28–56°C) higher than the diesel
PA. Higher temperature AGO !'/ PRODUCT
pumparound heat is easier to recover #RUDE OIL
against crude. Heat recovery and
fractionation compete against each
other. Increasing the AGO PA duty may -AXIMISE
EFFICIENCY
increase crude preheat, but it also reduces /PTIMISE
the reflux rate below the diesel product STEAM
draw, which lowers the diesel product
yield and increases the AGO product !TMOSPHERIC
yield. As the AGO product yield increases, RESIDUE
so does the amount of diesel boiling-
range material in the AGO. As crudes get
heavier and the flash zone vapour rate Figure 6 Atmospheric column stripping section
decreases, the AGO PA duty must be
reduced to maintain adequate diesel CDU should be designed without an remove any heat below the diesel
fractionation section reflux. When AGO PA because the amount of flash product draw and have a reasonable
processing extra-heavy crude oils, the zone vapour is so low it is impossible to fractionation section internal reflux

42 PTQ Q1 2009 www.eptq.com

 11th International Petrochemicals
IPTC 2009
Euro Petroleum Consultants
Technology Conference & Exhibition
16 & 17 February 2009, Royal Garden Hotel, London

IPTC’s expert speaker Following on from 10 years of continued excellence, IPTC 2009 will once
again be THE essential forum to be updated on current performance and
panel includes: future prospects for the global petrochemical industry, including implications
to supply and demand, industry profitability and the very latest developments
Michel Buffenoir in technologies for olefins, polyolefins, aromatics and derivatives.
CEO With engaging presentations from a highly talented speaker panel,
Technip interactive discussions and many social events designed to facilitate making
new business contacts, IPTC remains the unmissable event for all those
Dr Noor Jivraj working in the international petrochemical industry.
Senior Consultant
Jacobs Consultancy
“Thank you for an excellent conference.
Rainer Kemper A special thanks for all the support
General Manager which I have received from you when
Process Engineering presenting KataLeuna as one of your
Linde sponsors. Overall this conference was
successful in creating promising new
Paul Hodges projects.”
Chairman Dr. Martin Knoche
Sales Manager
International eChem
KataLeuna GmbH Catalysts

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Register at www.europetro.com, Tel: +44 (0) 20 7357 8394, Email: conferences@europetro.com

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Euro Petroleum Consultants
18 & 19 February 2009, Royal Garden Hotel, London

IDTC’s expert speaker At this 10th Anniversary Meeting delegates will be provided with a complete
overview of the main challenges and drivers for the global refining industry
panel includes: including the implications of low demand growth in Europe and North
America, the continued effect of the Middle East on global supply and the
Phil Packer new challenge of energy security.
Principal An expert speaker panel will present recent case studies to examine the
Nexant Limited latest technologies for clean fuels. The leading catalyst suppliers will discuss
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Development and insightful presentations and offered
MOL outstanding opportunities for meeting
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Ivan Souček
Licensing Director
Chairman of the Board of Directors and CEO
Exxonmobil ČESKÁ RAFINÉRSKÁ, a.s.

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 requires yielding more atmospheric
column diesel or modifying the VDU to
Ejectors
produce vacuum diesel. Raising the
atmospheric column diesel yield
demands better stripping, higher flash
zone temperature, lower column
operating pressure, higher diesel/AGO
fractionation section reflux or more
fractionation efficiency. In some
Vacuum diesel
instances, modifying the atmospheric
column may materially increase diesel
Optimum
efficiency { Optimum
reflux (L) recovery at a reasonable cost. Yet, in
other cases, modifying the atmospheric
LVGO (FCC feed)
column is very high cost, with relatively
V
small yield improvements.

Vacuum crude fundamentals

Maximising CDU/VDU diesel recovery
requires a diesel product draw on the
vacuum column. Yet only a few US
refiners produce a vacuum diesel
product. Most still produce FCC feed
MVGO (FCC feed) from the top side-draw product, and it is
not unusual for it to contain 60–80%
diesel boiling-range material. Many non-
US refiners already produce diesel
product from the top side-draw of the
Figure 7 Vacuum column diesel products vacuum column. Revamping an existing
column or designing a new VDU to
produce vacuum diesel requires a
fractionation section (Figure 7).
Ejectors Fractionation is inherently better in the
vacuum column because the L/V ratio is
much higher than the atmospheric
column. The top pumparound condenses
the vacuum diesel product and reflux (L)
for the fractionation section. Since the
reflux flow rate is low, it must be metered
Vacuum diesel and flow controlled to ensure it is
maintained within the distributor
limitations. Good control of the column
heat balance is needed to generate
sufficient fractionation section reflux.
LVGO (FCC feed)
The vacuum column diesel/LVGO
V
fractionation section L/V ratio is high
compared to the atmospheric column.
The fractionation section reflux rate is
typically 40–100% of the vacuum diesel
product rate. Since the vapour rate
leaving the top pumparound is extremely
AGO from low, the vapour rate to the fractionation
atmospheric
column MVGO (FCC feed) section is primarily vacuum diesel
product and LVGO product. While in
the atmospheric crude column, the
vapour rate leaving the diesel
pumparound contains overhead receiver
Figure 8 Maximum diesel product yield gas, naphtha and kerosene, as well as
the kerosene fractionation section reflux.
rate. Optimising the column heat atmospheric residue. The optimum Therefore, atmospheric column diesel
balance is critical to optimising the number of stripping trays is eight to ten. fractionation section molar L/V ratio is
internal reflux and diesel product yield. A customised rectangular tray designed typically 0.1 or less, whereas the vacuum
Stripping section performance is often at very high weir loadings maximises column fractionation section L/V ratio
overlooked when considering diesel efficiency and helps prevent fouling is 0.3–0.5. Since the vacuum column
product yield improvements (Figure 6). throughout the run length. Maximum L/V ratio is much higher than the
The stripping section vapourises the stripping section efficiency allows the atmospheric column, it has better
front end of the flash zone liquid as it diesel fractionation section reflux to be fractionation.
flows down through the trays. Improved increased. The optimum stripping steam The vacuum column pumparound
tray design and an increased number of rate is 5–8 lb/barrel of atmospheric heat balance determines the amount of
trays raise efficiency, increasing the residue, depending on stripping section vacuum diesel that can be produced.
amount of flash zone vapour and efficiency. The top pumparound duty must be
reducing the amount of diesel in the Higher CDU/VDU diesel recovery sufficient to condense the available

44 PTQ Q1 2009 www.eptq.com

vacuum diesel product and the internal reflux. It is not
unusual for too much heat to be removed in the lower

VLI_Petro_86_270_PTQ_08e.qxd
pumparounds, resulting in low vacuum diesel product recovery

Visual Level Indicators

even with a properly designed fractionation section. When
packing efficiency is adequate (~ three theoretical stages) but
the internal reflux is low, the vacuum diesel product yield will
be low. Fractionation efficiency alone will not provide high
vacuum diesel product recovery. Optimising the internal
reflux (L) allows the maximum amount of vacuum diesel
product yield.
Maximising CDU/VDU diesel product requires either no
AGO product from the atmospheric column, or the AGO can
be fed to the vacuum column to recover the diesel boiling-
range material. When atmospheric column AGO contains a
large amount of diesel, it must be fed to the vacuum column to
maximise overall recovery. Since the atmospheric column
operates above atmospheric pressure and vacuum below, the
majority of the AGO product vapourises when it enters the
vacuum column. It should be fed to the vacuum column below
the fractionating bed for maximum vacuum diesel product and

Petrochemical
energy recovery (Figure 8). Selecting the proper location is
critical. In a vacuum column with both an MVGO and HVGO
pumparound, it should be fed below the MVGO pumparound
for maximum heat recovery.

Conclusion
Atmospheric column diesel recovery is inherently difficult

Series
because the fractionation section molar L/V ratio is typically
less than 0.1, whereas in the vacuum column it is 0.3–0.5. It is
simply impossible to achieve high recovery without a diesel
product draw on the vacuum column. Fractionation basics
favour this solution. Thus, it is not surprising that the CDU/
VDUs are designed differently where diesel product is the
primary motor fuel and economics favour high recovery. Today
that should also include US refiners.
Atmospheric and vacuum column diesel product yield
should be optimised based on VDU performance and energy
recovery. High atmospheric column diesel recovery makes the
VDU feed heavier, reducing the VGO yield, especially with
heavy and extra-heavy crudes. Heat recovery and crude preheat ● Meets the design standard of the petro-
depend on atmospheric diesel and AGO product yield. Diesel chemical, hydrocarbon and LPG/LNG industries:
draw temperature is much higher in the atmospheric column – Fully ANSI/ASME design
compared with the vacuum column. Consequently, all the heat – Includes NACE requirements
duty needed to condense vacuum diesel and its internal reflux ● Reliable level indication without external
is lost to air and water, whereas all the condensing heat and
power with three functions in one device:
approximately half the product cooling heat are recoverable to
crude oil from the atmospheric column. – Liquid level indication
Modifying the vacuum column to produce diesel from the – Liquid level switch
top section can be a relatively low- to moderate-cost revamp – Liquid level transmitter
with a high return. Some vacuum columns can have a ● Equipment with optional bi-stable change over
fractionation section added within the existing vessel or on/off switches and linear or non linear
dimensions, while others require the top section of the column
transmitters (also as 2-wire systems
to be replaced. Since the top section diameter is small, often no
foundation changes are needed. In one case, the CDU/VDU
with 4…20 mA output, optional with HART®
diesel yield was increased by 40% by installing a new top ● CE-conform and EEx-approval
section on the vacuum column with an investment of less than ● For operating pressures from vacuum up to 400 bar and higher,
$5 MM. Furthermore, by increasing diesel recovery, some operating temperature from -196°C up to +400°C
refiners have been able to unload their FCC and hydrocracker, ● Densities > 0.3 g/cm3
allowing higher crude charge rates without exceeding these ● Closed floats for condensing liquids up to 350 bar operating pressure
conversion unit capacities.
● Construction in stainless steel grade 316/316L as standard.
Also possible in higher grades of stainless steel like 904L or Hastelloy®
and Inconel®/Incoloy®alloys
● Casing of indication rail in stainless steel

Scott W Golden is a Chemical Engineer with Process Consulting WEKA AG · 8344 Bäretswil · Switzerland
Services in Houston, Texas. He has authored more than 100 info@weka-ag.ch · www.weka-ag.ch
technical papers on revamping and troubleshooting refinery
process units. Golden holds a BS in chemical engineering from the ARCA Flow Group worldwide: Competence in valves, pumps & cryogenics
University of Maine and is a registered professional engineer in Armaturen AG

Texas. Email: sgolden@revamps.com

von Rohr

www.ptqenquiry.com
for further information
www.eptq.com PTQ Q1 2009 45
Raffinerietechnik englisch 20-11-2008_A4_PTQ.qxp 20.11.08 09:30 Seite 1

As an internationally renowned engineering

partner and plant construction company,
Uhde offers complete service packages from
the initial concept to the turnkey plant.

Uhde provides these services to refineries

around the world. Two of our main specialities
are naphtha and middle distillate processing.

In line with the trend towards improving the

quality of gasoline and diesel, our Edeleanu
Refining Technologies Division has executed
numerous hydrodesulphurisation projects
during the last few years. Several plants, not
only based on world-class technologies
supplied by well-known licensors such as

· Axens
· Haldor Topsoe
· Kellogg Brown & Root
· UOP

but also proprietary Edeleanu technologies

designed in co-operation with catalyst
suppliers such as Albemarle or BASF, are
currently under construction.

Middle Distillate Desulphurisation Unit for

Shell Deutschland Oil GmbH in Wesseling, Germany

The total capacity of all our naphtha and

diesel hydrotreating projects since 2001 now
exceeds 15 million tonnes per year. The
treated products meet the European Clean
Fuels Directive.

Isomerisation of light gasoline or gas conden-

sate yields another valuable blending compo-
nent for gasoline. Our Edeleanu Refining
Solutions in Refining
Technologies Division executes projects for
grassroots plants or revamps of catalytic
reformers for that purpose. Technologies

C5/C6 Isomerisation, PCK Schwedt, Germany

In keeping with our slogan Engineering with

ideas, we provide a comprehensive range of
supplies and services which extends from the
initial feasibility study and financing right
through to operation of the turnkey plant.

Uhde GmbH
Edeleanu Refining Technologies Division
Friedrich-Uhde-Str. 2
65812 Bad Soden
Germany
Phone +49 (61 96) 205 1715
Fax +49 (61 96) 205 1717
Uhde
www.uhde.biz A company of ThyssenKrupp Technologies
www.ptqenquiry.com
for further information

ThyssenKrupp
Visit us at
Frankfurt a.M., May 11 - 15, 2009,
Hall 9.1, Stand O32 - R40
 Online cleaning improves
operational excellence
Online cleaning, followed by degassing and decontamination, can result in a significant
reduction in downtime, increased run length, operation under cleaner conditions and
potential avoidance of a turnaround, leading to an increase in production

Marcello Ferrara
ITW

O
nline cleaning of refinery — Control during execution. reprocessable product and the washing
production units has been To these operational and fluids are compatible with the
positively proven in many organisational costs, huge production hydrocarbon processing industry/
severe applications such as the bottom loss costs must also be added, followed combustion process. As a result, the
section of visbreaker and vacuum by equipment downtime. Even more equipment can be put on-stream
columns with both trays and structured relevant are the costs associated with the immediately after cleaning.
packing. In turnaround applications, decrease in performance during the run. Another problem encountered during
visual inspection has confirmed positive Moreover, all these operations can suffer turnaround is the duration of steam-out
results. An entire unit can be cleaned from different problems, such as: operations and their associated
online in just 24–36 hours. Furthermore, — Long time for isolating/inserting the environmental problems, which directly
online cleaning can be implemented equipment impact equipment downtime.
during unit operations to recover unit — Waste generation
performance, operate under clean — Hydrocarbon emissions Current operations
conditions and improve operational — Bundle damage Mechanical cleaning is currently
excellence. — Difficulties in bundle extraction performed only where there is a stringent
— Difficulties in unbolting need for it. This suggests that equipment
Current cleaning technologies — Hazard to workers performing is being allowed to degrade to the
Today’s technology for cleaning heat mechanical operations minimum acceptable performance
exchangers includes the following — Hazard from scaffolding before cleaning. This situation arises
procedures: — Hazard from spills of carcinogenic from a number of peculiarities in the
— Flushing (R45) products hydrocarbon processing industry.
— Isolating equipment from the — Hazard to people working nearby First, the industry sees cleaning as a
process and blinding moving equipment/vehicles troublesome, lengthy operation that
— Removing hydrocarbons — Hazard from bundle transportation/ leads to a loss in production, so it is
— Steaming out for gas removal cleaning apparatus/cranes. avoided. Also, the mechanical cleaning
— Scaffolding Due to continuous improvements in process involves at least 20 operations,
— Unbolting process safety and environmental each of which has an associated hazard.
— Removing covers and distributor performances, these problems are now When the production/maintenance
— Extracting the bundle only acceptable when there really is no department faces a cleaning situation, it
— Transporting the bundle from plant other choice. normally reacts in one of two ways:
to washing area — The situation is fairly typical and
— Hydroblasting Safety and managed as a routine operation
— Transporting the bundle from environmental factors — The situation is problematic and
washing area to plant The hydrocarbon processing industry postponed until it can no longer be
— Inserting the bundle continues to try and limit airborne tolerated.
— Inserting new gaskets emissions through technical efforts In the first case, the management
— Installing covers and distributor and investment. For example, consider team is unlikely to consider something
— Bolting the investments and revamps required that is not routine. Or, in the best case
— Removing blinding (eg, valve substitutions, insulation of scenario, they will be excited about
— Removing scaffolding flanges, double seals on pumps and trying something new. However, unless
— Air removal and purging double seals on tanks) to limit volatile the management team is strongly
— Performing pressure tests organic compounds (VOCs), then committed to the necessary testing of
— Inserting the apparatus in the imagine the effects of hydroblasting on the new technology, there is a tendency
process. these assets. to procrastinate.
All of these operations have their Until recently, hydroblasting was the In the second case, the management
related costs. The bidding paid costs are only effective technology for cleaning team may not be innovative enough to
to be added to the customer’s heat exchangers and process equipment. look for a new technology and address
organisational costs in terms of: However, by performing cleaning the problem in a brute force manner
— Awarding (bid organisation, operations in a circulation loop, online that might eventually be inefficient and
evaluation and award) cleaning eliminates all the problems costly. In both cases, process unit
— Planning associated with hydroblasting. Moreover, economics and environmental
— Co-ordination sludge is converted to a fully reusable/ performance can suffer significantly.

www.eptq.com PTQ Q1 2009 47

 Industry mindset been successfully cleaned online. An Increasing revenues
In view of these factors and the currententire unit can be cleaned in 24–36 The following case histories may be
industry mindset when it comes to hours. The advantages online cleaning considered unusual by some; others may
cleaning process equipment, the cost has over hydroblasting include: see them as typical of the hydrocarbon
— Reduced downtime
benefits of online cleaning are significant. processing industry. Paradoxically, the
Budget compliance is a must in all — Closed loop operation, without the industry is not energy efficient. As
business units, which is why divergence need for extracting the bundles energy is so readily available, costs are
from a budget for long-term investment — Simultaneously cleaning of multiple not always taken fully into account.
is usually not an easy decision. units Another problem is that cleaning is a
The production, maintenance,— No waste generation lengthy and unsafe operation that can
environmental, investment — No emissions.
and lead to a loss in production, which can
administrative departments all have The ITW cleaning method involves overwhelm the energy-saving benefits.
separate budgets to which they must the injection of an oil-based chemical For this reason, cleaning is usually
adhere, and each department is that transforms sludge into a fully postponed until the last minute.
concerned only with their own budget. reusable product, thereby removing any Online cleaning helps to address
Of course, this reflects common practicesludge and deposits from metal surfaces. all production, energy-saving,
when running a company, but sometimes The washing solution can be reutilised/ environmental, safety and reliability
it is better to consider the company as a
reprocessed because the stabilising issues, as it can achieve equipment
whole, not as a collection of individualproperties of the chemical avoid closed loop cleaning for the entire
boxes. reaggregation of deposits, thereby production unit in less than one day,
Is it worthwhile increasing
eliminating any potential precipitation making equipment immediately
maintenance costs for the sake of during storage and/or fouling of process available for production.
increasing production, reducing energy equipment. Moreover, the patented In very difficult to solve cases, online
costs and improving safety, reliability,chemicals used in ITW’s method are cleaning can be performed during
environmental performance and
compatible with hydrocarbon processing different periods of the run to avoid
compliance? To date, this has not been industry/combustion processes, as they: certain problems. Depending upon the
— Do not contain any metals
the case, as there has been no technology magnitude of the problem and the
available for simultaneously increasing — Do not contain any compounds particular application, even coke
production, reducing energy costs and based on P, B, S, As, Bi, Si or Pb formation inside equipment (eg,
improving safety, reliability and — Do not contain any halogen columns, packings and exchangers) or
environmental performance. — Do not contain any compounds that delta P (∆P) build-up can be prevented
might be harmful to plant metallurgy by regular online cleaning.
Advantages of online cleaning — Do not contain any carcinogenic At current high crude oil costs and
However, an array of technologies are compounds high operating margins, being able to
now available for solving problems — Do not contain any compound that address all these issues can lead to
related to equipment cleaning, in operating dosages might interfere significant improvements in revenue.
including ITW’s patented technology with biological waste treatment For example, by reducing the amount of
for cleaning heat exchangers and processes. fuel burned, there will be a reduction in
process equipment in a closed loop. After online cleaning, the heat SOx, NOx, CO, CO2 and other airborne
Equipment can be cleaned online with exchangers can be immediately put back pollutants at no extra cost. When
this technology without having to on-stream without extracting the considering all the investments the
extract the heat exchanger bundles). bundle. However, if visual inspection is hydrocarbon processing industry is
This is particularly beneficial in severe to be performed, a clean bundle can be implementing to reduce airborne
applications such as visbreakers and extracted. The hard coke will dry if it is pollutants, online cleaning can provide
ptqana third page filler 10/12/08 12:27 Page 1
columns with structured packing present, as the technology eliminates all the following advantages:
internals. Crude distillation units the coke binders, and is friable and very — Reduced waste generation
(CDUs) and vacuum units have also easily removed. — Reduced VOC emissions

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aspect of Refining, Gas or Petrochemical Processing?

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Simple as that

48 PTQ Q1 2009 www.eptq.com

— Reduction in airborne pollutants
(following energy savings and reduction
in fuel burned)
— Reduced CO2 emissions (following
energy savings and reduction in fuel
burned)
— Improved safety.
It is important to note that the health,
safety and environment benefits are
achieved without any extra investment
or cost. The cost of installing spare
equipment is avoided too. However, the
greatest benefits of online cleaning are
increased run length, operation under
cleaner conditions and potential
avoidance of a turnaround.

Turnaround operations
improvement
A technology is also available that uses a
patented chemical, added during steam-
out, to significantly reduce steam-out
time and hence unit downtime. The
chemical also eliminates any noxious
odours during steam-out, as well as any Figure 1 Visbreaker bottom exchanger
pyrophoric iron problems. The ITW
patented chemical does not create any
emulsion either.
By applying online cleaning followed
by degassing/decontamination there is
little, if any, need for mechanical
cleaning, and safe entry conditions are
achieved more quickly. This results in a
significant reduction in downtime,
which in turn leads to an increase in
production.

Alternatives
There are instances where online
cleaning technology was considered
from the onset as an alternative to
mechanical cleaning or to improve
turnaround operations. This was due to
the fact that the operator required
visual inspection to validate the
technology. As a result, online cleaning
was implemented during the actual run
to immediately recover unit
performance, to run under cleaner
conditions and increase run length. It is
therefore used as a preventive tool for Figure 2 Visbreaker main fractionator bottom
unit optimisation and to improve
operational excellence. Achievable
revenues from these optimisations
depend upon unit configuration and
production layout. They will certainly 4OPPING
reach several million dollars if applied
proactively. 6AC UUM

Climate conditions and 6ISBREAKER

cleaning schedules 6AC UUM 4) 
In many countries, very cold or very hot SECTION
climate conditions often dictate the
time for any process unit cleaning )'##
activity. As a result, refineries may be 0REHEAT 3TORAGE
forced to tolerate inefficiencies until BOTTOM TANK
TRAIN
climate-related conditions permit.
However, climate conditions only affect
those mechanical cleaning techniques
such as hydroblasting that are lengthy
and labour and equipment intensive. Figure 3 Online cleaning of Visbreaker vacuum bottom section: layout of refinery

www.eptq.com PTQ Q1 2009 49

 Climate-related factors do not affect
online cleaning to the same degree. ITW
technology only requires 24 hours on a
Visbreaker vacuum section bottom train outlet temp.
310 oil-to-oil basis, normally two engineers
Average and no heavy hardware, just the
290
recovery chemical and the injection pump.
270 The improved flexibility in solving
Temperature, °C

250 operational problems is discussed in the

following case histories.
230
210 Case study 1
190 Online cleaning of a visbreaker
Mechanical cleaning
of 2 shells Online cleaning Online cleaning was performed during a
170
scheduled decoking of the furnaces after
150
0 20 40 60 80 100 120 140 160 180 200 220
one year’s operation of a European
Days on stream refinery’s visbreaker unit. Cleaning of
the exchangers was originally not
scheduled, as the unit may bypass the
critical preheat exchangers, allowing for
Figure 4 Online cleaning of visbreaker vacuum bottom section: recovery of outlet mechanical cleaning during the run.
temperature Here is a summary of the results:
— In 36 hours, 28 bottom exchangers
of a 310 tph visbreaker were cleaned
— The bottom of the main fractionator
VB–E2 outlet temperature (quench temp.) was clean (normally about 1m of sludge
290 and coke is found)
VB–E1 mechanical Average — The bottom packing of the main
cleaning recovery
270 fractionator was clean
— Furnace decoking time had been
250 reduced by about 20%
Temperature, °C

— The visbreaker started up 12 hours

230 before the scheduled time, with all the
preheat, packing and lines clean (which
210 were not in the cleaning schedule).
Visual inspection of the most severe
190 Online
cleaning service bottom exchanger was performed
Before ITW to validate the results. However, the
170 After ITW
Lineare (before ITW)
other bottom/preheat train equipment
150
was not opened. Figure 1 shows the
visual inspection of the first bottom
n
an

24 b
14 b
ar

19 r

7- r
25 y

12 y
30 n
un

14 ul

1- g
19 p
ep

25 t
12 ct
ov

c
Oc
Ap

exchanger cleaned after one year in

a
a

De
Ja

u
Fe

Se
-J

-O
-M

-A
M
-M

-N
-J

-J
-J
-F

-A

-S
1-

7-
1-

27
6-

9-
19

operation. Figure 2 shows the bottom of

the main fractionator at the manway
opening.
Figure 5 Simultaneous online cleaning of vacuum and visbreaker units: recovery of
visbreaker quench temperature Case study 2
Online cleaning of visbreaker
vacuum section bottom train
Online cleaning was applied to the
vacuum section of a visbreaker. The
VV–H1 inlet temperature
290 layout of the refinery with this visbreaker
Online is shown in Figure 3. The refinery’s
VB–E1 mechanical cleaning
270 cleaning problem was related to an increase in
the vacuum section bottom train’s
250 outlet temperature (reading TI1826).
The refinery usually cleaned the
Temperature, °C

230 exchangers when the outlet temperature

approached 280°C. It had to
210 Average mechanically clean two exchangers to
recovery
reach the targeted run length. However,
190 this did not recover the temperature, so
Before ITW the visbreaker was facing an unscheduled
170 After ITW shutdown to mechanically clean the
Lineare (before ITW)
entire vacuum section’s bottom.
150 To solve the problem, the vacuum
section bottom was online cleaned in 48
an

6- n
24 b
14 b
ar

19 r

7- r
25 ay

12 y
30 n
un

14 ul

1- g
19 p
ep

25 t
12 ct
ov

ec
Oc
Ap

a
a

u
Fe

Se
-J

-O
-M

-A
M
-M

-N

D
J
-J

-J
-J
-F

-A

-S

hours. The visbreaker was then started

1-

7-
1-

27

9-
19

up immediately. The temperature

recovery on TI1826 was on average
Figure 6 Simultaneous online cleaning of vacuum and visbreaker units: recovery of 45°C, which remained stable during the
vacuum furnace inlet temperature run (Figure 4). The unit could easily

50 PTQ Q1 2009 www.eptq.com

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reach scheduled turnaround and run
five more months (the full run is not
reported in Figure 4).

Case study 3
Simultaneous online cleaning of a
vacuum unit and a visbreaker
Online cleaning was applied to a vacuum
unit integrated with a visbreaker at a
European refinery. The reason for
considering online cleaning was the
increase in the visbreaker’s quench
temperature, which was limiting
throughput. Mechanical cleaning of
four heat exchanger shells (with the
hottest at the bottom) had not helped to
recover the temperature, so there was a
steady increase in quench temperature.
After being cleaned online, the two
units were started up in 36 hours. The
recovery of the quench temperature
was about 50°C (Figure 5), and as the
units are integrated a recovery of 18°C
on the vacuum furnace inlet temperature Figure 7 Online cleaning of slop distillation unit: main fractionator bottom before
was also achieved (Figure 6). online cleaning

Case study 4
Online cleaning of slop
distillation unit
A slop distillation unit processes, on a
campaign basis, all the slop collected
on-site at a 280 000 bpd refinery. The
facility has four topping/vacuum units,
one FCCU, one residue hydrocracker
and two ethylene units. After the one-
to two-month campaign, the slop
distillation unit is shut down for
cleaning, as it suffers from very heavy
fouling and coke accumulation.
To demonstrate the effectiveness of
online cleaning, the unit was run as
usual. It was then shut down and opened
to check the fouling conditions in the
main fractionator and two bottom
exchangers. The unit had about 1m of
coke-like sludge in the bottom of the
main fractionator. Moreover, the main Figure 8 Online cleaning of slop distillation unit: main fractionator bottom before
fractionator’s trays and bottom online cleaning
exchangers were heavily fouled.
The online cleaning lasted 24 hours.
Degassing/decontamination was then
implemented to reduce steam-out time,
eliminate any noxious emissions and
pyrophorics ignition. The main
fractionator bottom and trays were free
of any deposits, and some 1–2 kg deposits
were found in the bottom exchangers.
Fortunately, these deposits were loose
and easily removed using the unit’s
service water at 2–3 bar. No mechanical
cleaning was carried out on the unit and
it was henceforth started up. Figures 7
and 8 shows the situation before online
cleaning, and Figure 9 shows the
improvements afterwards.

Marcello Ferrara is the Chairman of ITW

S.r.l. in Augusta, Italy. Ferrara graduated
with a PhD in industrial chemistry from Figure 9 Online cleaning of slop distillation unit: main fractionator bottom after
Messina University in Italy. online cleaning

www.eptq.com PTQ Q1 2009 53

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 Increasing FCC yields
with oxygen enrichment
With the demand for diesel increasing faster than that for gasoline and other refined
products, an increase in FCC distillate yield can provide a low-cost route to capturing
margins opportunities. Oxygen enrichment can help to achieve these goals

Jack Olesen
Praxair

A
relevant question posed by study for a 30 000 bpd FCCU that was cracking catalyst system, the type of
refiners at the recent NPRA Q&A in planning to increase LCO make. molecules that are being cracked will
Orlando and the ERTC in Vienna Dropping the riser temperature 40°F and increase the coke make.
was concerned with how to configure lowering catalyst from 71 MAT to 63
the FCCU towards higher distillate-to- increased LCO by 3%, but CSO also Air blower constraints
gasoline ratios. Other related and equally increased by 5%. This is probably not a If there is no additional capacity in the
important issues were concerned with good economic trade-off. air blower, options to remedy this
ways to manage light cycle oil (LCO) To provide better economic trade-offs, constraint include:
production, bottoms recycling and the changing the catalyst matrix activity to — Diverting some of the heavier FCCU
use of oxygen enrichment to improve compensate for a lower riser temperature feed to a hydrocracker
FCCU profitability. and other previously noted changes has — Adding more air blower capacity
been considered. However, in this case, — Using oxygen enrichment to
Straight-run diesel recovery when making the previously discussed supplement the air blower.
Considering the importance of major changes and raising the matrix surface When implementing oxygen
diesel-producing units in today’s market, area by 80 m2/g, LCO did indeed increase enrichment, the refiner should first
such as the hydrocracker, higher diesel by 4%, but CSO increased even more determine if there are any permitting
yields are also possible with FCC than the LCO. The larger volume of CSO issues related to emissions or allowed
operations. The first thing a refiner can be mitigated by taking a heavy cycle coke burning rates. Praxair has supplied
should consider is how much straight- oil (HCO) draw and sending that stream oxygen enrichment systems for over 25
run (SR) diesel is in the combined feed to the hydrocracker, if one is available. years and is currently supplying about
to the FCCU. It is not unusual to find up Otherwise, the refinery should consider 20 FCCUs. In the past, the reasons for
to 20% diesel-range boiling material in recycling the fractionator bottoms (ie, enrichment were to increase feed rate or
the FCC feed, and the target should be bottoms recycling), preferably the HCO conversion, have the ability to process
to get this down to 5%. SR diesel does portion if that can be drawn off heavier feedstocks, or reduce regenerator
not crack that well in the FCCU and the separately. velocity for increased time between
quality of the LCO is worse than the turnarounds.
quality of the virgin diesel going into Bottoms recycling
the unit. Then there are the obvious While bottoms recycling was practised Oxygen enrichment levels
operational changes that can be made in the past before high-activity zeolite In terms of the range of possible
on the unit, such as lowering catalyst catalysts were available, this option may enrichment levels, most of the FCCUs
activity, increasing the matrix surface re-emerge into a future trend. Why? If supplied by Praxair enrich to 23–28%
area (lower Z/M) and reducing the riser there are going to be substantial increases oxygen, although levels up to the mid-
temperature. in LCO make, recycling HCO, or 30% have been reported. Praxair has no
recycling HCO plus CSO (if there is no specific oxygen enrichment limit and
Trade-offs: higher separate HCO draw), will almost always we treat any enrichment that results in
CSO production have to be considered. The recycle greater than 23.5% oxygen as if the
The trade-offs in pursuing this route (ie, should be injected into the riser through system were exposed to pure oxygen.
reducing severity to increase LCO separate nozzles that are preferably For most units, the practical enrichment
production) are that the main located above the fresh feed injection limit becomes the regenerator
fractionator bottoms, often referred to nozzles. At the same fresh feed rate, the temperature or the ability of the
as slurry or clarified slurry oil (CSO), FCCU will have to be able to handle the downstream recovery system to handle
increase at a faster rate than the LCO. additional volume from the recycle and the higher charge rate and conversion.
These increases are at the expense of have sufficient air blower capacity to The regenerator temperature limit has
gasoline and LPG. If the reduction in deal with the increased coke make. often been addressed with a catalyst
LPG or alkylation unit feed is a concern, Of concern is the increase in slurry at cooler. For situations where there is 20%
the refiner should consider using a lower conversion unless the recycle recycle, oxygen enrichment is very
ZSM-5 additive. stream is put into service. The recycle practical. For example, in the previously
In order to quantify these changes, stream can be as high as 20% of the discussed case, the level of enrichment
one must first bear in mind that, as with fresh feed rate. This volume of recycle is required was about 23%.
everything in FCC operations, these necessary to keep the CSO make constant Therefore, taking into account all of
changes will be unit specific. For relative to the higher conversion base the previously noted issues surrounding
example, Praxair recently completed a case. Even with a coke-selective bottoms bottoms recycling and LCO production,

www.eptq.com PTQ Q1 2009 55

 a certain level of LCO increase can be available, it would realistically take a site for installation of liquid oxygen
expected. Referring again to the about nine months to implement. There tanks and a vapouriser. The timing to
previously discussed case that Praxair are the usual permitting and HAZOP build an air separation unit is currently
studied in detail, the change in LCO was processes that need to be handled first. about 24 months. Praxair builds, owns,
from a base case of about 10% to about The equipment involved is relatively operates and maintains the unit and
18%, while keeping the CSO constant. simple and consists of an oxygen then sells the oxygen directly to the
However, Praxair did not model the use metering skid, an oxygen flow controller refiner. The oxygen cost is competitive
of ZSM-5 to keep LPG make constant. tied into the control room with the cost of pipeline oxygen.
instrumentation to control and monitor There is concern with regard to an
Implementation the process effectively and safely, and expected octane drop in the FCC
While the increase in LCO at constant the injection quill that goes in gasoline at reduced unit severity, which
CSO and 23% oxygen enrichment is downstream from the main air blower is another reason to consider ZSM-5 to
very attractive, refiners may nonetheless (MAB). If there is no oxygen pipeline, maintain FCCU gasoline octane and
be concerned with the amount of time the refiner would have to consider a keep the alkylation unit full.
required to implement oxygen liquid oxygen system or an on-site air
enrichment. This depends on whether separation plant. Timing for liquid Impact on emissions
the refiner is close to an oxygen pipeline oxygen would be similar to the pipeline It is well understood that NOx reacts
or not. Where pipeline oxygen is case. In addition, there would need to be with CO to produce N2 and CO2. With
oxygen enrichment, there is less inert
nitrogen in the regenerator and hence
the CO partial pressure is higher, leading
to reduced NOx. As for SOx, if the refiner
is using a SOx additive, the performance
should increase. This is because the SOx
additive captures the SO3 and the higher
oxygen partial pressure drives the SO2
to SO3.
With regards to future CO2 limits and
carbon capture and sequestration (CCS)
requirements, the development of
“green FCCUs” may become a possibility.
Praxair is looking into this topic in co-
operation with FCC licensors, since we
have a lot of history with CO2 handling
due to the acquisition of Liquid Carbonic
several years ago. To be sure, while the
equipment we are accustomed to may
be similar, the operation might be
dramatically different.

Petrochemical interface
Oxygen enrichment does not only apply
to FCCs, but also to sulphur plants for
capacity expansion or backup purposes
and process heaters for improvements in
efficiency and throughput. In addition
to oxygen, hydrogen is supplied either
by pipeline or by on-site steam methane
reformers (SMRs).
More recently, a process for reducing
NOx and or CO coming out of the
regenerator is in development. This
process would have application in
meeting emission requirements for full-
burn or partial-burn units. In the
petrochemicals arena, hydrogen is being
recovered and purified, which might
otherwise be burned as fuel. In the next
issue of PTQ, a detailed article on energy
and hydrogen utilisation audits will be
featured.

Jack Olesen is Senior Business Development

Manager for Praxair in the US Gulf Coast
region. He has over 30 years’ experience in
the industry. Olesen earned a BS degree at
University of California Irvine, and MS and
PhD degrees in chemistry at University of
Colorado. Email: jack_olesen@praxair.com

www.ptqenquiry.com
for further information
56 PTQ Q1 2009 www.eptq.com
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 Attention all FCCU operators
The FCCU in transition
How refiners can benefit from an unprecedented opportunity

Pre-eminent FCC expert, Warren Letzsch, and PTQ’s editor, Rene Gonzalez, have
co-authored an important new study with the single objective of informing refiners how they
can make their FCC unit operations more profitable. Topics covered include:

l How recent projects have generated major financial advantages by

converting HVGO from the latest generation deep cut vacuum
distillation units (See section 6.1 of the Study)

l How to provide a balanced output of clean burning gasolines and

ULSD gas oils while optimising chemical hydrogen consumption
and minimising outputs of lower value (See section 6.1)

l How larger refineries can explore parallel conversion opportunities

for heavy distillate conversion (See section 6.1)

l How modifications to major refinery assets, such as the vacuum

unit, delayed coker and MHC will directly benefit FCC operations
(See section 6.6)

l How refiners who have successfully increased diesel and/or

propylene production from their FCC unit are succeeding in
obtaining better separations from their FCC main fractionators (See
section 8.1)

l How best to benefit from changes in heat and energy balances

resulting from an increase in the size and complexity of regenerator
units (See sections 2.3, 4.1, 6.3 and 6.5)

l How proposed legislation for carbon capture and sequestration

mandates will affect FCC design, including details of CO2 capture
from conventional SMR plants and polygeneration gasification
plants, allowing the regenerator to operate on ambient air w/o CO2
capture (See section 6.5)

l How full-burn units are performing at higher severities processing

opportunity feeds but still meeting current and future emissions
targets (See sections 2.3 and 7.3)

l How to get the greatest productivity out of FCC/RFCC and l A survey and refinery wish list of selected FCC unit components
associated gas plants, particularly when linked to: including feed nozzle injectors, cyclones and steam strippers (See
° Mild hydrocracking unit (MHC) sections 12.4, 12.5 and 12.6)
° Butylene alkylation unit
° Two-stage desulphurisation unit l Survey of rotating equipment developments for improving reliability
° High purity propylene plant of new and refurbished WGCs and MABs (See section 11)
° Separate draws within main fractionators
° Integrated slurry oil filtration unit l Process flow diagrams showing FCC units configured for specific
° Third-stage separator with underflow filtration (See section 8.2) product objectives (export-based refineries, refineries targeting
WCS feedstocks, FCCUs with turboexpander/cogeneration
capacity) (See figures 1.1, 5.1, 7.1 and 7.2)
Plus
l Survey of future long-term trends affecting FCCU process design
l Assessment of FCC catalyst formulations for processing and operations, including market and regulatory trends such as
hydrotreated cat feeds and non-hydrotreated cat feeds (See higher fractions of heavier feeds, synthetic blends and biomass
sections 6.7 and 9) processed through the FCC. (See sections 13, 14.1 and 15)

For further details of the contents of this study and

how to purchase it, go to www.eptq.com/studies
 New roles for FCCU: carbon
capture unit and coke gasifier
Environmental and energy security concerns may evoke new roles for the FCCU in
addition to the production of liquid fuels and light olefins. Gasification and
carbon capture are two such possibilities

Erich J Mace, Adrienne M Blume and Thomas W Yeung

Hydrocarbon Publishing Company

F
luid catalytic cracking has been Obama has repeatedly warned, “Global of which petroleum refining claims
evolving since the first unit was warming is not a ‘someday’ problem 19.8% (277.6MM mt/y in 2002)
commissioned at Esso’s Baton — it is now,” and supports a carbon of the emissions. Excluding the
Rouge refinery in 1942.1 Today, it cap-and-trade scheme that would combustion of refinery fuel, the
continues to be a unit in transformation, require greenhouse gas (GHG) emitters FCCU is the largest emitter of CO2 in the
adapting to increasingly heavier feeds, to either buy pollution permits or refinery.3 Regenerator flue gas is almost
strict transportation fuel specifications, reduce emissions directly from their exclusively the source and can comprise
product demand changes and unit operations. Refiners will initially spend anywhere from 15–50% of refinery CO2
emissions standards. their extra capital on emissions permits emissions.4 Since it is the largest non-
The FCCU is traditionally configured rather than plant expansions, but as fuel-derived source in the refinery, it is
to produce gasoline for maximum yield, CO2 credit prices rise they will need to in refiners’ interest to investigate FCCU
maximum octane or maximum octane consider making energy efficiency CO2 reduction methods. A study released
barrels as needed, but its role is changing. improvements and capturing CO2 from by Petrobras in 2003, shown in Figure 2,
For example, gasoline demand, although major emissions point sources. Analysts details the distribution of refinery CO2
still growing worldwide, is on shakier assert that the introduction of a US cap- emissions.5
ground due to biofuels mandates that and-trade scheme would foster the As the coked FCC catalyst is
require certain percentages of gasoline development of such low-carbon regenerated via combustion, the
to be replaced with ethanol and the technologies. Outside the US, Canada’s following important model reactions
recent economic turmoil that has Conservative government expressed occur (reactions 1–10). Coke and CO
dampened consumption. Refiners are interest in Q4 2008 in forming a climate combustion (reactions 3 and 6) are the
finding value in other FCC products, change pact with the US and, in the EU, chief contributors to flue gas CO2. Thus,
such as propylene and LCO, and units 2008 saw the adoption of a plan to if the combustion of catalyst coke can be
running on lower-quality feeds, such as implement CO2 permit auctions starting reduced (and carbon leakage within the
resid, are becoming increasingly in 2013. EU refiners will begin refinery does not occur), refiners can
common. Environmental regulations purchasing 20% of their permits by decrease CO2 emissions. Also, notice
have also shaped the current state-of- auction, transitioning to 100% by that the standard heats of reaction for
the-art, with flue gas systems and catalyst 2020.2 Such moves by Western nations reactions 1, 3 and 6 are large and
additives now standard to mitigate NOx, may also put pressure on countries like exothermic, supplying the bulk of the
SOx, PM and CO emissions and meet China and India to invest in similar heat for the FCCU:
reformulated gasoline requirements. technologies.
The aforementioned impetuses are According to the US Energy 1. 2C + O2 → 2CO, ∆Hºrxn = -221.1 kJ/mol
certainly enough to continue to foster Information Administration (EIA), the 2. C + CO2 → 2CO, ∆Hºrxn = 172.4
technological development in fluid US emits approximately 6.0 billion mt/y kJ/mol (reverse Boudouard reaction or CO2
catalytic cracking. However, the current of CO2. The manufacturing sector reforming)
geopolitical climate suggests a new wave produces 1.4 billion mt/y of that total, 3. C + O2 → CO2, ∆Hºrxn = -393.5 kJ/mol
of FCC developments is on the horizon,
potentially transforming the unit into a
polygen operation including fuels
production, petrochemical production,
syngas production, power generation, 'ASOLINE
./X 3/X
and carbon capture. Figure 1 compares 0- 0OWER 'ASOLINE
the current roles of the FCCU to its REDUCTION
future roles. #/ ,#/
Modern CAPTURE Future
FCC 3YNGAS FCC 0ROPYLENE
Impending legislation
In the US, President Barack Obama’s 2ESID ,#/ ./X 3/X 2ESID
environmental platform seeks to cut UPGRADING UPGRADING
0-
CO2 emissions to 1990 levels by 2020, REDUCTION
0ROPYLENE
curb emissions to 80% below 1990
levels by 2050, and require fuel
producers to decrease the carbon
content of their fuels by 10% by 2020. Figure 1 Future roles of fluid catalytic cracking

www.eptq.com PTQ Q1 2009 59

 combustion and partial combustion
reactions also occur. The following
40 reactions, along with reactions 1, 2, 3,
35 34.20% and 6, are those central to gasification:12
30.20%
30 27.60% 11. C + H2O → H2 + CO, ∆Hºrxn = 131.3
kJ/mol (water-gas reaction)
25
12. C + 2H2 → CH4, ∆Hºrxn = -74.9 kJ/mol
Percent

20 13. CO + 3H2 → CH4 + H2O, ∆Hºrxn = -206.2

kJ/mol
15
14. CO + H2O → CO2 + H2, ∆Hºrxn = -41.1
10 kJ/mol (water-gas shift)
15. CO2 + 4H2 → CH4 + 2H2O, ∆Hºrxn =
5 2.70% 2.30% 1.80% -165.0 kJ/mol (methanation)
0.51% 0.46% 0.189% 0.09%
0
es CU n. n. ia ne
s r y re or
s rs As seen in Figure 3, the resulting
ac FC ge ge on i ve Fla ot he
rn m H2 m rb co M Ot
Fu ea Am Tu r re syngas evolving chiefly from reactions 2
St u
l ph and 11 can then undergo Fischer-Tropsch
Su (F-T) synthesis or water gas shift (WGS).
If the syngas undergoes WGS, H2 and CO2
Figure 2 Refinery CO2 emissions are produced, and the CO2 can be
sequestered and/or recycled back to the
4. C + H2O → CO + H2, ∆Hºrxn = 131.3 gasification typically requires regenerator to improve the rate of the
kJ/mol temperatures ranging from 1400–2800ºF reverse Boudouard reaction. The
5. C + 2H2O → CO2 + 2H2, ∆Hºrxn = 90.2 (760–1537ºC) at pressures anywhere additional production of hydrogen has
kJ/mol from atmospheric up to 1000 psig obvious benefits for energy and
6. CO + 1/2O2 → CO2, ∆Hºrxn = -283.0 (7 MPa).11 The defining difference hydroprocessing needs. A dry gasification
kJ/mol between gasification and combustion is — ie, gasification that operates on a high
7. 2H2 + O2 → 2H2O, ∆Hºrxn = -483.7 that significantly less air/oxygen is CO2/O2 ratio vs a high H2 O/O2 ratio —
kJ/mol
supplied during gasification. Thus, a would be advantageous for CO2 capture.
8. S + O2 → SO2, ∆Hºrxn = -296.8 kJ/mol
reduction in oxygen concentration If F-T products are produced from the
9. 2SO2 + O2 → 2SO3, ∆Hºrxn = -197.7
along with pressure and temperature syngas, both the liquids and the wax can
kJ/mol
modifications can shift an FCCU conceivably be fed back into the FCCU
10.  N + xO → NOx, ∆Hºrxn (dependent
on x and minor in unit heat balance regenerator from a combustor into a for upgrading. Or, as has been proven by
calculations) gasifier, producing syngas (CO and H2) companies such as Sasol and Shell, diesel,
instead of CO2 and H2O. One way to gasoline, wax and high-quality olefins
achieve gasification conditions is to are obtainable for direct use, depending
Gasification of FCC reduce oxygen content by increasing the on F-T catalyst choice and process
catalyst coke CO2/O2 ratio or the H2O/O2 ratio in the conditions. Alternatively, the syngas can
Several efforts, including work by BP regenerator air feed. This action improves be used as a combustion fuel for a gas
and UOP, suggest that one method to the rates of the two key gasification turbine, as is the case with integrated
shift selectivity away from combustion reactions: the water-gas reaction gasification combined cycle (IGCC)
reactions is to operate the regenerator in (reaction 11) and the reverse Boudouard applications.
gasification mode.6,7,8,9,10 Operating reaction (reaction 2). A heat supply is The reverse Boudouard reaction is
conditions for an FCCU regenerator are also required to shift the thermodynamic particularly advantageous because it
typically 1250–1500ºF (675–815ºC), equilibrium of these endothermic consumes CO2. It can be achieved at
with pressures near atmospheric reactions to products. Typically, this normal FCC regenerator temperatures
pressure. For comparison, coal heat is supplied when the exothermic with the addition of particular metals to
the FCC catalyst. Li and Na have been
observed to be most active in increasing
the rate of the reverse Boudouard
reaction, where a 1 wt% addition of the
two metals in an undisclosed proportion
Spent FCC H2 for fuel or
catalyst FCCU catalyst Syngas CO2, H2 Absorption/ hydroprocessing yielded approximately 60% coke
WGS
regenerator/
reactor
adsorption/ conversion at 1400ºC. Equilibrium FCC
coke gasifier membrane
catalyst, containing metals deposited
F-T liquids during FCC operation, has also been
and wax to Concentrated
FCC feed cited as having high activity for the
CO2 CO2
Highenthalpy

F-T CO2 reverse Boudouard reaction.10 The

recovery compression
Regenerated process (optional) endothermic reverse Boudouard reaction
feed

FCC catalyst
may be particularly useful for RFCC
FCC dry gas
units, where higher Conradson carbon
feeds produce a surplus of heat in the
Gas High-quality
turbine products regenerator. Typically, this heat is
removed by catalyst coolers or other
heat removal equipment.
Air Recycled CO2 for gasification
Maintaining unit
heat balance
As was previously mentioned, the full
Figure 3 FCC gasification overview and partial combustion of catalyst coke

60 PTQ Q1 2009 www.eptq.com

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supplies the majority of heat for the the effect of water on FCC catalyst at — In a multiple-stage scheme of
FCCU. If coke is gasified instead of elevated temperatures and pressures may varying CO2/O2 ratios, can the unit
combusted, the heat balance will be cause more extensive hydrothermal maintain a heat balance or will additional
disrupted. A potential scheme to deactivation of FCC catalyst. In this case, heat be needed (eg, gas turbine effluent
maintain the heat balance would be to the fresh catalyst makeup might increase. or heat exchanger)?
remove part of the coke by traditional If multiple regenerator stages are
oxidative methods, as well as a certain necessary to control the unit heat balance Additional feeds
percentage via gasification. The catalyst and fully regenerate catalyst, refiners If the FCCU can become a profitable
could enter a first regeneration stage, may find the capital cost too high. syngas producer, other feeds may also be
where it is contacted with a higher CO2 Should WGS be employed, a separation fed directly to the regenerator to increase
/O2 feed to undergo gasification, system to remove CO2 from the product syngas production. For example,
subsequently entering a second stage stream will be needed. Capital costs and residuum, coal, pitch or biomass-derived
where oxidation can fully regenerate plot space will also come into play here. feeds could be fed into the dilute-phase
the catalyst and provide ample heat for Some additional unanswered questions transport line of the regenerator vessel
the unit. The CO2 created by the are summarised below: to be gasified. Biomass-derived material
oxidative stage can then be recycled to — Will FCC catalyst be satisfactorily can play another role in gasification.
the gasification stage. This concept regenerated? Instead of a traditional air-fed FCC
could be extended to several — Will afterburning become more or regenerator, current research has
regeneration stages of varying CO2/O2 less of an issue due to high CO concen- suggested that oxygenates fed over
ratios. More stages would give operators trations but lower O2 concentrations? coked FCC catalyst may be sufficient to
more control over the unit heat balance — Is it possible to catalyse the reverse produce syngas and regenerate catalyst
and the extent to which the catalyst is Boudouard reaction without poisoning in a multi-stage process, minimising the
regenerated. Alternatively, lower-carbon the FCC catalyst? addition of air.14 This process may allow
heat sources might be used to close the — Can catalytic material such as Li be refiners to meet biofuels mandates via a
unit heat balance if less coke is incorporated into the FCC catalyst new avenue. Specifically, biomass-
combusted. For example, dry gas from matrix, or will particles need to be added derived oxygenates could offer a clean
the FCCU could be used to heat the gas into the cracking catalyst circulation, oxygen source, avoiding the
feed to the regenerator, thus supplying thus diluting base catalyst; or are Ecat disadvantages of N2 inherent in air
a high-enthalpy stream to heat the unit metals sufficient catalysts? combustion to produce syngas as a
and provide heat for the endothermic — What sort of H2O and CO2 partial valuable byproduct.
gasification reactions. This option pressures in the regenerator are
would be a significant departure from advantageous, and will CO2 separation Future contributions
current FCC methodology, since the and compression become hurdles? from the FCCU
coke yield is not fixed by the unit’s heat — For RFCC applications, can The refining industry is very likely
balance. gasification consume enough heat to headed toward a necessary retooling of
Gasification also requires water, and avoid the need for catalyst coolers? how it conducts business in light of
environmental legislation, demand
shifts and crude oil volatility. The FCCU
has been remarkable in fostering
★

ingenuity among engineers and

scientists for seven decades and, in
3rd light of the present situation, the stage
is set for new developments to emerge.

refining
The unit may now be viewed as a
potential polygen operation, producing
fuels, syngas and perhaps power, while
also performing CO2 capture. Syngas

China
★

★
can be used to synthesise F-T products
for sale or for further upgrading in the
★ FCCU. Alternatively, it can be converted
to methanol and subsequently to

2009
★ gasoline via a methanol-to-gasoline
(MTG) process. Under certain
★ conditions, syngas can also be shifted
to create a concentrated CO2 stream,
although what to do with this CO2

17–18 March 2009

stream is still under debate. Ideally,
geologic storage is to be avoided, since
this method permanently removes

Beijing potentially useful carbon, although it is

better than expelling CO2 into the
atmosphere and can be useful for
enhanced oil recovery. Using CO2 to
The networking event of the year for everyone synthesise profitable materials is
with an interest in refining technology in China. perhaps a better long-term option,
albeit an extremely challenging one,
Combine it with a visit to CIPPE, 19-21 March since CO2is already in a very favourable
thermodynamic state.
Despite this hurdle, progress in
www.refiningchina.com
utilising CO2 has been made in the areas
of polymers (BASF and Novomer),

62 PTQ Q1 2009 www.eptq.com

 methanol production (Princeton rint?articleId=USL2141355220080121. 12 Gasification, www.zero.no/transport/bio/
University) and algal systems to produce 3 Creek T, CO2 management role of gasification.
carbon capture, 2003 European Refining 13 O’Connor P, Corma Camos A, Huber G,
fuels (Shell and Chevron).15,16 Perhaps it Processing of biomass-derived oxygenates
Technology Conference 8th Annual
would even be profitable to produce CH4 Meeting, London, 17–19 Nov 2003.). with particles comprising a coke deposit,
via CO2 methanation if the prices for H2 4 Schuette G, Latimer E, Cross J, Esen E, WO 2008/006904, 17 Jan 2008.
Evaluating CO2 Capture Options for a Fluidized 14 Tuillo A, Capturing carbon, Chem. Eng.
and CH4 were right along with other News, 23 June 2008, 86, 21.
Catalytic Cracker Regenerator, National
economic conditions. Finally, the FCCU Energy Technology Laboratory, www.netl. 15 Science & technology concentrates:
can potentially provide power to units doe.gov/publications/proceedings/06/ making methanol from carbon dioxide
carbon-seq/Tech%20Session%20026.pdf. and sunlight, Chem. Eng. News, 19 May
other than itself through the installation 2008, 86, 40.
of a gas turbine on the regenerator feed, 5 Chamberlin O, Gilbert W, Cerqueira H,
Rawet R, Pimenta R, Moure G, Rocha P,
not to mention the power recovery An integrated approach for oil industry
opportunities available on regenerator through heavy oil conversion, hydrogen
flue gas and steam letdown streams. If production, CO2 sequestration and Erich J Mace is Technology Analyst with
enhanced oil recovery, 18th World
syngas is used to power the gas turbine, Petroleum Congress, Johannesburg, South
Hydrocarbon Publishing Company in
the FCCU could become a sort of IGCC Africa, 25–28 Sept 2005. Southeastern, Pennsylvania. He has a
unit. It is already known that the FCCU 6 Rong Y, Zhang N, Jobson M, A novel BSCHE degree.
is a complex unit, but it has the potential regeneration process for reduced CO2 Adrienne M Blume is Managing Editor
emission, AIChE Spring National Meeting,
for even greater complexity. In providing New Orleans, 6-10 April 2008. with Hydrocarbon Publishing Company
more functions to maximise the utility of 7 Hedrick B, Towler G, System and method of in Southeastern, Pennsylvania, and has
each carbon atom that enters the unit, it recycling spent catalyst in a fluid catalytic published various articles in the trade press,
cracking unit, US Patent Application 20
can enable refiners to better position 080 152 552, 26 June 2008.
as well as having participated in various
themselves for long-term success. 8 Towler G, Rundell D, System and method detailed industry-related studies. She has a
reducing carbon dioxide emissions in a master’s degree in English and publishing.
fluid catalytic cracking unit, Australian Email: ablume@hydrocarbonpublishing.
This article is based on selected material from Patent Application AU2007254596, 20
Dec 2007. com
Hydrocarbon Publishing Company’s latest
multi-client strategic report entitled, Future 9 Mayes J, Warden W, Method of Producing Thomas Y Yeung is Principal Consultant
roles of FCC and hydroprocessing in modern Synthesis Gas From a Regeneration of with Hydrocarbon Publishing Company
refineries. Spent Cracking Catalyst, US Patent 6 585
884, 1 July 2003.
in Southeastern, Pennsylvania, and has
10 Hettinger W, Kovach S, Hoffman J, published various articles in the trade press,
References Endothermic Removal of Coke Deposited as well as participated in various in-depth
1 Wilson J, Process Overview, Fluid Catalytic on Catalytic Materials During Carbo- industry-related studies. He is a registered
Cracking, PennWell Publishing Company, Metallic Oil Conversion, US Patent 4 425
259, 10 Jan 1984. professional engineer and holds BSCHE,
Tulsa, OK, 1997, 1–6.
2 Ennis D, EU to phase in CO2 auctions for 11 Jenkins S, IGCC 101, www.gasification. MSCHE and MBA degrees. Email: tyeung@
refinery, airlines. www.reuters.com/articleP org/library. hydrocarbonpublishing.com
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840316 Shell Q&A 297X210.qxd 4/12/08 15:55 Page 1

START WITH RIGHT

THE
RIGHT ANSWERS

QUESTIONS
IT,S A STATEMENT OF THE OBVIOUS, BUT IN
OUR EXPERIENCE, IT,S ONE THAT OFTEN
GETS OVERLOOKED – PARTICULARLY
WHEN THE QUESTIONS BEING TACKLED
MAY BE HIGHLY COMPLEX. OUR GETTING
TO THE HEART OF SOMETHING COMES
FROM BEING ABLE TO PUT TOGETHER AN
INTEGRATED TEAM FROM DIFFERENT
BACKGROUNDS – ONE THAT SPECIALISES
IN ASKING THE RIGHT QUESTIONS.
THIS PRETTY MUCH SUMS UP HOW WE
WORK, BOTH AMONG OURSELVES AND

THE WITH OUR CLIENTS.

REAL SOLUTIONS FOR THE REAL WORLD.

www.shell.com/globalsolutions

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for further information
 Oil sands
industry status
The steady progress made in the oil sands industry up to Q3 2008 will eventually
resume. For now, an examination of the favourable market conditions and
upgrading scenarios that are required for future profitability are presented

Tony Pavone
SRI Consulting

A
s of year-end 2008, global crude clean coal, biofuels, alternative renewal costly to produce than conventional oil.
oil supply and demand were in energy, nuclear, and non-conventional So although the world may not be
tight balance, resulting in the fossil fuels. approaching “peak oil”, it is much
rapid increases in crude oil prices and more likely to be approaching “peak
price volatility between 2007 and 2008. Global crude oil producers cheap oil”.
As marker crude West Texas Intermediate Russia, Saudi Arabia and the US are the Canadian tar sands, Venezuelan tar
(WTI) exceeded $145/bbl in mid-2008, largest producers of crude oil in 2008. sands, oil shale, deep offshore oil, sub-
the world began to see a moderation of The greatest concentration of production salt oil, GTL (gas to liquid fuels), BTL
demand growth caused by high prices. (both oil and gas) is in the Middle East. (biomass to liquid fuels) and CTL (coal
Crude oil demand actually decreased in Shown in Figure 1 are the top ten to liquid fuels) chemistry are expected to
the US, Western Europe and Southeast producer countries. represent cumulatively at least 3.0
Asia, while demand growth moderated trillion barrels of higher cost crude
in the fast economic growth BRIC (Brazil, Global proven crude oil resources.
Russia, India and China) countries. oil reserves What the world seems to be running
Global crude oil demand growth of 2% Since the discovery of crude oil in the out of is light, sweet crude oil that can
per year, which had characterised 2000– late 19th century, the world has be produced at both low costs and at
2006, was cut nearly in half by 2008 consumed approximately 1.0 trillion low business risk. Much of the
by the cumulative impacts of higher barrels of crude oil. There are sufficient conventional crude resource oil is
petroleum prices, lower global GDP, quantities (1.0 trillion barrels) of proven located in politically unstable countries
and mandated production and use of conventional crude oil reserves (Russia, Middle East and West Africa),
biofuels. According to the US Department (determined by drilling) to meet today’s which adds a price premium to the cost
of Energy (DOE): “The combination global demand for another 25 years. of production. Figure 2 presents the
of rising global demand, fairly normal There are expected to be another 2–3 conventional proven crude oil base of
seasonal inventory patterns, slow gains trillion barrels of unproven conventional the major producers by country
in non-OPEC supply, and low levels of crude oil reserves, such as the heavy of origin.
available surplus production capacity Venezuelan and Canadian crudes, and In this crude oil supply constrained
is providing firm support for prices.” shale oil, which are together much more environment, producing oil from
Note that claims in some quarters
that high oil prices were being driven by
futures market speculation (dry barrel
participants), profiteering by oil
companies and the withholding of 6ENEZUELA
supply by OPEC are conspicuously
5!%
absent from this government assessment.
During the 2007–2008 period, geo- #ANADA
political concerns over some major oil
supplier output (Nigeria, Iraq and .ORWAY
Venezuela) have contributed to oil price -EXICO
volatility.
Over the longer term, primary global #HINA
energy demand is expected to increase
)RAN
by 50–60% by the year 2030, driven
primarily by population growth and the 53!
desire for better living standards. The US
3AUDI !RABIA
National Petroleum Council, an
organisation of US oil companies 2USSIA
reporting to the US president,
acknowledges that conventional oil and      
gas alone are unlikely to satisfy this --BPD
demand growth in its seminal 2007
report, and called on the development
of supplemental energy sources such as Figure 1 Top ten global crude oil-producing countries

www.eptq.com PTQ Q1 2009 65

 Forms of unconventional
oil resources

Synthetic crude oils
 Canadian tar sands
Extra heavy oil (Venezuela)
 Shale oil (mostly western US)
" ILLIO N B B L

 Synthetic fuels

Coal to liquids (CTL)
 Gas to liquids (GTL)
Biomass to liquids (BTL)

Renewable fuels
 Biodiesel/green diesel
 Bio-based ethanol/cellulosic ethanol
T

! L IL
N

2U N

.O C O
+U Q

AY
#A !
A

Z A E LA

IA

.I A
R IA

DA

- IA
!%
AI

AZ
BI

IN
BY
) RA

A
) RA

53

R
SS

RW
ST

I
W

GE

GE
NA
5
+ A EZ U

#H

EX
RA

"R
,I
KH
I!

N
UD

6E

Table 1
3A

Figure 2 Crude oil reserves by country Current Alberta tar

sands capacity
According to the Canadian Association
of Petroleum Producers, actual
production in 2007 for tar sands-derived
crude oil had increased to 1.1 MM bpd.
Venezuela
Besides this producer organisation,
Canada Alberta’s Energy Resources Conservation
Saudi Arabia Board has produced its own assessment
of provincial tar sands current and
Russia
forecast capacity. Their claim is that
Iran 2007 production of 1.32 MM bpd
Iraq will more than double by 2017 to 3.23
MM bpd.
Kuwait
Due to the increasing capital cost to
UAE develop tar sands projects, a number of
Kazakhstan projects have attracted additional equity
participation by firms not currently
Libya
involved in Canadian tar sands.
USA Occidental Petroleum has bought a 15%
Nigeria interest in Total’s Joslyn project.
Over the period between 1999 and
China 2006, it is interesting to note that most
Mexi co of the growth in tar sands capacity has
Algeria been in steam injection as opposed to
Oil surface mining. Once bitumen is
Norway Bitumen
produced, it has to be pipelined to
market. Since bitumen is too thick and
0 100 200 300 400
viscous to be pipelined, it can either be
Billion bbl
diluted with lighter material (naphtha,
kerosene or middle distillates) or
Figure 3 Distribution of conventional vs bitumen resources upgraded. Upgrading involves chemically
converting bitumen into pumpable
Canadian tar sands is one of several bitumen is concentrated in Russia, synthetic crude oil via either carbon
sources of the world’s next-generation Canada and Venezuela. rejection (coking) or hydrogen addition
energy supply base, especially for The DOE has prepared a segmented (hydrocracking).
transportation fuels. Canadian tar sands forecast of global petroleum production Between 1999 and 2006, oil sands
have approximately 175 billion barrels from non-conventional liquid fuels, as upgrading capacity in Canada more
of proven oil reserves (estimated via shown in Table 1. than doubled and is nearly 1.0 MM
drilling) and 1.5–2.5 trillion barrels of Of these non-conventional petroleum bbl/d. This upgrading capacity can be
unproven reserves (estimated via sources, Canadian oil sands are forecast compared with conventional oil refining
computer modelling). to have the greatest volume impact, capacity in Alberta, which is half
with a forecast production rate of 2.9 that capacity.
Heavy vs light crude oil MM bbl/d in 2030 under modest oil The economic incentive to develop
The distribution of conventional crude price assumptions, or 4.9 MM bbl/d Canadian tar sands production is shown
oil versus the bitumen contained in under a high oil price scenario. Looking in Figure 4, which presents estimated
Canadian tar sands for major oil- at other sources of non-conventional oil industry expenditures for tar sands. This
producing countries is shown in Figure (synthetic and renewable fuels), none information was prepared by the
3. Most of the crude oil found in the has the potential impact of oil sands on Canadian Association of Petroleum
Middle East and Western Hemisphere is substantially increasing the world’s Producers. Annual capital expenditures
conventional, while most of the supply of fuel. topped C$10 billion in 2005 and

66 PTQ Q1 2009 www.eptq.com

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 upsets from water slugs and
other unpredictable situations
that have damaged internals,
resulting in diluent losses and
high vacuum unit overhead con-
densable oil. Diluent is neither
cheap nor plentiful, and high
vacuum column operating pres-
sure will reduce overall liquid
volume yields. And if the design
of the delayed coker fractionator
is based on today’s experience
with conventional heavy feed-
stocks you will be lucky to run
six months.
What all this means is that
special process and equipment
designs are needed to satisfy
the special demands of pro-
cessing oil sands crudes. Such
processes are not generated by
computer based designers who
have little or no experience and
never leave the office. They are
developed only by engineers
Oil Sands Crude with know-how who have real
experience wearing Nomex® suits
– Profits and feedstocks are extremely hard and measuring true unit per-
to desalt, difficult to vaporize,
Problems? thermally unstable, corrosive, and
formance in Northern Alberta.
Shouldn’t this be kept in mind
produce high di-olefin product by those considering long term
Canadian bitumen production from the coker. If you intend to supply agreements?
currently runs about 1 MMbpd, lock into a long-term supply,
with some being sold as Synbit therefore, it is imperative that you
and Dilbit. Over the next 10-12 consider reliability and run length
years output is expected to from a particular design.
increase to 3.5 MMbpd and more
refiners will begin investing to Too low tube velocity in the
process it and come to depend vacuum heater tubes will lead to
on the Synbit and Dilbit for a precipitation of asphaltenes. Too
significant part of their supply. fast a flow rate will erode the
Few today, however, have ever tube bends. If coil layout, burner
processed these feeds at high configuration and steam rate are For a discussion of factors
blend ratios, and are unaware not correct, run length will be involved in designing refinery units
that conventional process and measured in months, not years. to process difficult oil sands feed-
equipment designs are not up Diluent recovery unit designs stocks, ask for Technical Papers
to the job. Canadian oil sands must take into account possible #234 and 238.

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increased almost 50% the following
year.
Although the rising price of crude oil,
such as we saw in the first half of 2008,
increases the economic incentive to 2006
produce Canadian tar sands, the capital
2005
costs for developing tar sands projects
have also increased substantially, 2004
doubling from 2001 to 2008.
2003
Upgrading tar sands
Most upgraders use delayed coking as 2002
their primary mode of carbon rejection.
2001
Coking is the high temperature, ambient
pressure cracking of carbon-carbon 2000
chemical bonds in a non-catalyst
reaction (thermal cracking) to form two 1999 Capital spending, $C-billion
primary products: solid delayed coke
that is nearly hydrogen free, plus gas oil 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0
that has the desired carbon-to-hydrogen Billion bbl
ratio. Gas oil is further hydrocracked to
produce a diesel-rich product stream,
then mildly hydroprocessed for sulphur Figure 4 Estimated capital expenditures for Canadian tar sands
removal. Some upgraders substitute fluid
catalytic cracking for hydrocracking, — Crude oil price as it affects tar sands The feverish activity in Canadian tar
resulting in a product stream that is project economic viability sands interest since 2004 is tied directly
gasoline rich rather than diesel rich. — Hydrogen and utility cost inputs to with the quadrupling of nominal crude
tar sands production oil prices since 2004. As the crude oil
Proposed tar sands projects — The capital cost of production and product price increases, the economic
The Canadian Association of Petroleum processing facilities incentive to upgrade tar sands increases
Producers anticipates the addition of — Environmental impacts of tar sands even faster.
significant tar sands capacity between development: Whether tar sands economics can be
2008 and 2020, with just over 1.0 MM – Surface disturbance viable at prices well below $100/bbl for
bbl/d in 2008 to nearly 3.5 MM bbl/d in – Disposition of tailings new capacity is not known, and will not
2020. Its forecast includes significant – Greenhouse gas emissions be known until the current slate of
additions to capacity from both surface – Water consumption projects are completed and their as built
mining and drilling (in-situ) production – Potential aquifer contamination economics known. One developer
using injected steam. Of the alternative — Logistical and infrastructure (Total) has indicated a breakeven price
methods, in-situ production is expected requirements of about $90/bbl for projects under
to grow at a much faster pace than — Producing tar sands below natural consideration in 2008.
conventional mining methods. Details gas reservoirs
of specific tar sands production and — Long-term storage of by-product Business risk
upgrading projects follow, as of year-end sulphur Compared to other crude oil-producing
2008: — Socio-economic impacts on native regions in the world, it should be
— North West Upgrading will install an communities. reinforced that Alberta tar sands
upgrader in Sturgeon County, Canada, development does not present some of
capable of upgrading 77 000 bbl/d of Crude oil price the major political and socio-economic
bitumen. The upgrader will use delayed Producing Canadian tar sands is issues that surround crude oil producing
coke gasifiers provided by Lurgi, and a significantly more costly than producing elsewhere. Such factors are difficult to
hydrocracking unit utilising LC-Finer conventional crude oil from a simple quantify as business risk compared to
(Lummus Chevron) technology model of cost to extract. However, tax better understood technical and
— Besides western Canada and and royalty conditions in some economic risk. The benefits of producing
Venezuela, commercial heavy oil jurisdictions often result in an economic crude oil in Canada include:
developments have been considered (or environment for an operating company — Canada does not present the
are occurring) in Iran (Soroosh-Nowruz where its actual cost becomes far higher cultural, security and terrorism issues
fields), Oman (Mukhaizna field) and than simple production cost (because of rampant in the Middle East
Brazil (Marlim Sul and Jubarte) these taxes). As a result, Canadian tar — Canada does not present the political
— Occidental Petroleum has taken a sands economics, when compared to stability issues associated with West
15% share of Total’s Joslyn project for other tax and royalty environments, can African producers such as Nigeria and
$500 MM, replacing co-owner Enerplus be more desirable. Unfortunately, below Angola
Resources. a certain nominal price of oil, Canadian — Canada does not present the ethnic
tar sands are not economically viable cleaning and social issues prevalent in
Issues impacting Canadian even if there are no royalty considerations. countries like the Sudan and hot spots
tar sands development For existing tar sand producers with such as Darfur
Several issues will impact the pace of depreciated assets that were built when — Canadian democratic institutions
development of tar sands production the cost of construction was far lower are not threatened by oil money
capacity in Alberta, Canada. At some than it is today, that breakeven point is influence as in Russia and some of its
point, these same issues are likely to thought to be somewhere around $25/ former republics
impact heavy oil and non-conventional bbl. For new, grass-roots projects, the — Most Canadian tar sands are likely
crude oil development elsewhere. The breakeven point may be closer to to be shipped by pipeline, which is
primary issues are: $100/bbl. inherently safer than oil tanker

www.eptq.com PTQ Q1 2009 69

 transport: Exxon Valdez (Alaska), Prestige payout that was indexed to price rather uncertainty of Alberta’s royalty position.
(Galacia), Amoco Cadiz (Brittany) than profitability. S-H will proceed with its bitumen-
— Canadian tar sands do not present The problems that all governmental producing facility, but avoid upgrading
the safety and environmental risks agencies have in levying royalty regimes until the business risks with royalty rates
associated with offshore oil production: to reflect fair economics is that specific are resolved. Oil consultant Wood
Piper Alpha (North Sea), Ixtoc-1 project economics are only one MacKenzie has also evaluated the impact
(Mexico) component of the decision-making of increasing royalty revenue and
— Tar sands development has less process by the proponent. Although the predicted a $26 billion reduction in tar
environmental and social impact on economics of a specific project can be sands investment.
endangered species, migratory herds reasonably estimated by third parties, Another approach by the government
and the lives of indigenous peoples the decision of a particular proponent to in Alberta is to avoid royalty cash
compared to competing forms of the pursue a particular development project payments from tar sands, and instead
world’s energy supply. depends on the attractiveness of a special accept its share of royalty in the form of
project (its return on investment) and in-kind bitumen. The provincial
Tax environment on how those economics compare to government has advertised for offers to
Prior to the current activity, tar sands other global opportunities available to a upgrade a portion of its bitumen to
development had virtually stopped after proponent. If developing project higher valued products, such as synthetic
the first two large projects (Suncor and opportunities in the Middle East or West crude oil or petrochemicals.
Syncrude) became operational. There Africa represent a better business deal,
was some development work by Exxon/ then that is where development money Capital cost escalation
Imperial (Cold Lake) and Shell (Peace will flow. As the price of crude oil has dramatically
River), but little additional commercial Unfortunately, estimating the increased, so have other basic commodities
production. economics of other projects in other used to produce oil and gas. These include
The original tax environment was a regions is speculative at best. As a result, structural steel, heavy wall (high pressure)
1% tax on production revenues until governments pursue a specific royalty fabricated steel vessels, corrosion-resistant
the capital investment had been paid regime and observe the outcome. Higher alloys, other base (copper, nickel, zinc)
back, and then 25% of net profits after royalties in the North Sea have caused and precious (platinum, palladium,
payout. In 1997, the province created its operators to go elsewhere to pursue rhodium) metals, concrete and wood.
an Alberta Royalty Review Panel to better opportunities. At the extreme, This has resulted in global construction
recommend changes. Their nationalisation in Venezuela and Bolivia costs doubling between 2001 and 2008,
recommendations, which were modified has stopped outside development and higher levels in Alberta, where
by the government, resulted in altogether. In Alberta, StatoilHydro (S-H) shortages of skilled labour, construction
maintaining the 1% fee prior to payout, has already delayed a decision on equipment and infrastructure have
and a percentage of revenues after building an upgrader based upon the exacerbated the situation. As a result,

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70 PTQ Q1 2009 www.eptq.com
some proposed tar sand projects have This represents 0.19% of global energy
been deferred and will have their “The most obvious CO2 emissions, while supplying 3% of
economic viability tested later. global energy supply. This ratio is due to
opportunity for CO2 the much higher CO2 intensity of coal-
Current and potential mitigation (beyond better based energy production and use.
environmental impacts Greenhouse gas emissions (GHGs) from
Tar sands that have been produced via process technology) is tar sands development are three to four
surface strip mining are required to have times higher than from conventional
to recompress and
the surface area restored to near-original wells, but conventional oil wells pose
state at the completion of each project. re-inject CO2 back into other environmental issues that have
The first certificate for land reclamation been raised by the eco-activist
was issued to Syncrude Canada for a 104
hydrocarbon-bearing community.
hectare parcel known as Gateway Hill subsurface layers” The most obvious opportunity for
approximately 35 km north of Fort CO2 mitigation (beyond better process
McMurray. When mined, producing technology) is to recompress and re-
one barrel of bitumen consumes inject CO2 back into hydrocarbon-
approximately two metric tonnes of two years), some of the contained water bearing subsurface layers (either tar
tar sands. will separate into an upper layer that can sands or conventional reservoirs). CO2
Permits for surface mining of be decanted and recycled to the process. has been historically used by the crude
Canadian tar sands require that disturbed Once de-watered, the remaining tailings oil industry in tertiary oil recovery (also
areas be reclaimed after the bitumen has will stabilise over time, and can then be known as enhanced oil recovery [EOR]).
been removed. While the industry covered with muskeg and replanted. CO2 re-injected into subsurface reservoirs
claims it conducts a continuous process However, during the period that the reduces the viscosity and density of the
of mine reclamation, environmental tailings ponds are exposed at their surface, hydrocarbon liquids, lowers their
activists such as the Environmental wildlife (especially birds) will sometimes adhesion (surface tension) to the
Integrity Project claim the tailings ponds be attracted to and land on the ponds, surrounding sedimentary rock, and
represent: “Twenty square miles of non- causing high levels of mortality. One of increases the oil flow rate to the well.
reclaimable toxic lakes of mining waste, the challenges is therefore to manage Within western Canada, the Weyburn
making them some of the largest active tailings ponds while minimising demonstration project in Saskatchewan
manmade structures on the planet.” impact to wildlife. is examining the performance and
The debate on whether the surface A related problem is mature fine predictability of design parameters used
above the tailings ponds can or cannot tailings, representing a decanted water for CO2 enhanced oil recovery.
be restored to its natural state can only layer that is rich in stable (caused by
be settled by deeds rather than words. ionic charge) clay particles that form Water consumption
There is also a concern that migrating suspensions that are extremely difficult Approximately two to three barrels of
birds that land on active tailings ponds to separate. Surfactant treatment to water are needed to produce one barrel
are likely to be poisoned and die. The reduce charge and agglomerate mean of bitumen. This compares favourably
operating companies will have to address particle size can help, but advanced with the consumption of 100 bbls of
the issue of near-term impact, as well as technology is needed to adequately water to produce one barrel of fuel-grade
surface reclamation long-term impact. separate the clay from the water. ethanol. Although surface water supply
While Syncrude claims to have Another environmental concern over in Alberta is limited, large amounts of
reclaimed 22% of its mining area by replanted tailings ponds is how the final produced water accompany in-situ oil
2006, it is now seeking formal recognition surface is graded and what is used for production, while mined tar sands
by the province for its Gateway Hill replanting vegetation. Since most of the contain 10% water by weight. In the
recovery efforts. A reclamation issue stripped original surface is boreal forest future, water supply for tar sands
without a clear answer is how to manage on sloped terrain, the desire by some for recovery may be developed from
the environmental trade-offs in restoration to its original state provides subaquifer brine layers. Tar sand
purposeful reclamation. One a technical and economic challenge. operators have undertaken efforts to
environmental side wishes a restoration Since the stability of de-water tailings recycle nearly 100% of the water
effort that maximises biological diversity, ponds may not allow steep terrain to be consumed, minimise unit consumption
while another wishes restoration to created on restored mining areas, some of water and utilise (when economically
near-original conditions, while a third government guidance will be needed to justified) air-fin heat exchangers rather
would prefer a restoration plan designed establish the desired end condition and than cooling water towers for process
to maximise natural carbon capture the means to accomplish it. heat removal.
through the planting of high growth
vegetation. These three alternative Greenhouse gas emissions Cogeneration
environmental objectives are mutually The production and processing of tar Due to the high costs of producing and
exclusive. sands generates significantly more CO2 processing tar sands, the potential exists
than conventional oil production due to for using some of the tar sands or their
Tailings disposal the higher energy intensity required for processing derivatives (tar and delayed
The tar sands processed for bitumen steam injection of in-situ deposits and coke) as fuel sources to provide both
recovery use primarily hot alkaline water mining of surface and near-surface electricity and process steam. Since
and/or steam to displace the hydrocarbon deposits. Since all heavy crude oils are solids-based cogeneration requires
from the surrounding inorganic material. hydrogen deficient, hydroprocessing relatively new and capital-intensive
Since the inorganic material tends to be requires additional energy consumption technologies (gasifiers, particulate filters,
rich in clays, it swells upon grinding and for converting natural gas to hydrogen, acid gas extraction, steam and
wetting to form a semi-solid material that or alternatively producing hydrogen via combustion turbines, and boilers), the
is difficult to de-water. The current coal or coke gasification. According to scale for individual tar sands facilities
approach is to create bottom-sealed estimates made by the Pembina Institute, may not be large enough to be
tailings ponds to receive the tailings. tar sands production in ten years is economically competitive. However, to
Over an extended period of time (up to likely to generate 67 MM tpy of CO2. some extent, these liabilities are counter-

www.eptq.com PTQ Q1 2009 71

 balanced by the continuous demand environmental organisations (most requires extensive modifications to
load for both process steam and power. prominently the Pembina Institute and process Canadian syncrudes, it may be
the Environmental Integrity Project) subject to other environmental
Synthetic crude oil have reported that oil refineries provisions defining these changes as
composition planning on processing Canadian constituting a new source of pollution.
The synthetic crude oil produced from syncrude are likely to emit more Again, environmental activists are likely
Canadian tar sands can be one of two pollutants (SOx, NOx, particulates and to file lawsuits claiming that the
basic compositions. The most easy to heavy metals) than if they were to processing of Canadian syncrude
produce is a bitumen-rich mixture process more conventional light and violates legal provisions designed to
diluted with conventional refinery sweeter crude oils. Since refineries are minimise pollutant emissions.
blend stocks (LPG, naphtha, kerosene required to adopt best available If these challenges are perceived by
or gas oil). Alternatively, the synthetic technology for pollution abatement, it tar sand operators to be serious
crude oil can be a fuel in which the is likely that environmental activists challenges to the use of their product,
bitumen has been chemically altered will file lawsuits to prevent conventional the likely outcome is for the operators
(via carbon rejection and/or hydrogen refineries from making the modifications to expand the severity of their upgraders
addition) to more closely resemble necessary to process Canadian to incorporate severe hydrocracking
light, sweet crude oil. A number of syncrudes. If an existing refinery that would remove most of the
troublesome pollutants at the upgrader
rather than at the oil refinery.

Long-term storage of

it works… by-product sulphur

Since tar sands contain a high
concentration of sulphur (3–5 wt%),
upgraders first convert the sulphur
bound to carbon atoms in the bitumen
to hydrogen sulphide (H2S), then
convert the H2S to high purity sulphur
in solid yellow form (usually pills or
flakes). Given the low market price of
sulphur (<$100/mt), there is little
economic incentive to ship it from
Alberta to markets. Instead, producers
cast molten liquid sulphur into large
solid blocks, then store the blocks in
bulk earthen containers. The design life
for this form of storage is approximately
25 years, after which regular monitoring
is used to detect degradation. If
observed, the blocks are physically
sealed (usually in plastic) and stored
indefinitely.
The concern by some people is that
these sites may be abandoned after the
economic life of the tar sands project is
over, with the potential for subsequent
degradation that will result in releases to
the environment. The Alberta Energy
Resources Conservation Board (ERCB)
has several standards for the management
Kurita‘s ACF Technology of sulphur blocks in long-term storage.
is the unique solution to prevent ammonium An alternative approach is to eliminate
the Claus/Stretford processing of H2S to
salt fouling and related corrosion
solid sulphur and instead inject the H2S
Salt removal during normal operating conditions without (plus the CO2 acid gas that often
shutdowns accompanies it) into deep subsurface
Chemical solution with simple installation and low reservoirs, where it is unlikely to cause
investment cost contamination of ground water supplies.
Applicable at all refinery units with ammonium salt If a particular operator wishes to capture
problems the exothermic heat of combustion of
Proven technology and economical way to minimize H2S, he can alternatively burn the H2S to
process problems SO2 in a heat recovery steam generator,
then inject the SO2 into the subsurface
First choice for prevention of ammonium salt fouling or
corrosion reservoir.
Lastly, some effort is being made to
Find out more about Kurita‘s Kurita Europe GmbH find new commercial market outlets for
innovative technologies sulphur. Shell Oil is developing both
Industriering 43 · D 41751 Viersen
Phone: +49 2162 9580110 sulphur-containing concrete and
Fax: +49 2162 40159 sulphur-containing roadway asphalt.
www.kurita.de Both dispositions provide a large
potential sink for excess sulphur, if the
Anzeige PTQ 120x190_final.indd 1 06.06.2008 9:46:16 Uhr
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72 PTQ Q1 2009 www.eptq.com
properties of the end use product are
acceptable.
120
Availability of natural
gas feedstock Syncrude
Due to the high consumption of energy Bitumen
to produce tar sands, the availability of 100
natural gas fuel at competitive prices

Cumulative fraction distilled

would substantially improve the overall
economics for producing synthetic crude 80
oil. Natural gas is used both as a fuel and
as a feedstock in tar sands production. In
fuel mode, natural gas is used to produce 60
the steam required for in-situ production
of tar sands and to heat the hot water
required to separate the hydrocarbon 40
from the surrounding sandstone
material. Natural gas is also used in fuel
mode to generate the electricity required 20
to drive reciprocating equipment
(pumps, compressors and centrifuges).
In-situ injection steam is used to release
the hydrocarbons (tar sand) from the 0
0 30 220 345 550
surrounding rock and sand formations, Temperature, °C
as well as to heat the tar sands warm
enough to reduce their viscosity to a
level that can flow easily into Figure 5 Distillation curve of bitumen vs synthetic crude oil
recovery wells.
As a feedstock, natural gas is of natural gas is available, producing H2 gas from these sources to market have
chemically reformed (steam methane from natural gas becomes both the been stymied by economic and social
reforming) to produce the hydrogen economically and environmentally issues. However, if either or both natural
that is required in upgraders for preferred option. Compared to using gas pipeline systems are built, it is likely
hydrocracking and for desulphurisation natural gas as a fuel and feedstock, using that both proposed pipeline systems
via hydroprocessing. As a feedstock, coal or coke produces nearly twice as will pass close enough to Alberta’s tar
natural gas is the most energy-efficient much GHG emissions for a specified sands deposits to provide a new source
way to produce the hydrogen (H2) that is amount of hydrogen produced, or steam of natural gas at attractive prices. If
necessary to both crack open heavy and/or power raised. market prices for the gas are set in the
molecules and remove the sulphur The excess amount of natural gas US Midwest (Chicago), netback prices
contained in those heavy molecules. produced in Alberta that was formerly of the natural gas to Alberta should be
The cracking process consumes H2 by pipelined to foreign markets in the US is considerably lower.
saturating carbon-carbon chemical no longer in excess and no longer
double bonds. The sulphur in heavy available at low cost. As a result, tar Market pricing of tar sands
bitumen is converted to H2S by reaction sands producers in Canada are either Synthetic crude oils derived from tar
with H2. The H2S is then oxidised to pure buying high-priced natural gas or using sands and other heavy hydrocarbons
molten sulphur end product, with its H2 some of the tar sands product as a are priced at a significant discount to
converted to water (H2O). If natural gas substitute for natural gas. benchmark crude oils that are both
for reforming is not available, or not There are market indications that the lighter (lower viscosity) and sweeter
available at competitive prices, H2 must natural gas availability situation in (lower sulphur content). In order to
then be produced by cracking open Alberta may change with time. upgrade synthetic crude oils from tar
water molecules via gasification (partial Enormous quantities of natural gas are sands to the same yield of clean refined
oxidation), which is highly energy known to exist on the Alaska North fuels (gasoline, kerosene and diesel),
intensive. Slope and along the McKenzie Valley in significantly more refinery processing is
As a H2-deficient fuel, tar sand bitumen Canada’s Northwest Territories. required. Refinery heating oil has
can be converted to a pumpable liquid Recovering gas from both sources would similar physical properties as kerosene
fuel by either rejecting carbon (by require very long pipelines. Projects and diesel, and is used as a proxy for
coking) or by adding H2 (hydrocracking). announced thus far to transport natural kerosene and diesel in the options
The preferred option currently is delayed marketplace.
coking. However, as catalyst technology A simple distillation yield comparison
improves the economies for H2 addition, (Figure 5) of tar sand-derived synthetic
this option may become the dominant “As a H2-deficient fuel, crude oils vs bitumen shows that
technology, requiring additional tar sand bitumen can be approximately one-quarter of synthetic
amounts of H2 feed that normally is crude oils is composed of heavy
sourced from natural gas through converted to a pumpable molecules that boil above 400°C, while
reforming. almost 60% of bitumen boils above that
liquid fuel by either
Supplying the energy required for tar temperature.
sands recovery results in enormous rejecting carbon (by Nearly half of tar sand-derived crude
production of GHGs. If a low enough oils are composed of heavy molecules
cost fuel is available, such as coal or
coking) or by adding H2 boiling above 400°C. Since more capital
delayed coke, operators may select this (hydrocracking)” cost and more operating cost is required
option despite its GHG implications. to convert tar sands-derived crude oils
However, if a relatively low-cost source into acceptable clean refined fuels, the

www.eptq.com PTQ Q1 2009 73

 reduce the business risk of operating a
refinery. What started out as business
 risk insurance for refiners in the futures
market has changed radically to one in
 #RUDE OIL LIGHT  MEDIUM which most of the participants today
#RUDE OIL HEAVY have no relationship to oil refinery
 #RUDE BITUMEN operators and instead trade refinery
 crack spread options to make money.
 # M T

The dry barrel options market trades


approximately ten barrels each day to
 one barrel of wet barrels (actual oil)
produced by the refining business.

When traded (contract to buy or sell),
 the refinery crack spread price becomes
the exercise or strike price used to buy
 or sell the options contract.
*AN &EB -AR !PR -AY *UN *UL !UG 3EP /CT .OV $EC

Petrochemical potential for
tar sands
Figure 6 Historic pricing of Canadian crude oil Approximately 10% of the petroleum
produced worldwide is converted to
petrochemicals, with most of the
balance used for transportation fuels. A
small amount is used in power
80
production. The fundamental feedstocks
70 used to produce petrochemicals from
crude oil are refinery by-products LPG
60 and naphtha, and a smaller quantity of
natural gas production by-product
50
natural gas liquids (NGLs). NGLs are
$ US/bbl

40 primarily composed of ethane, propane,

butane, pentane and some hexane.
30 These fundamental petrochemical
20 Crude oil, light & medium feedstocks are converted primarily to
Crude oil, heavy olefins (ethylene, propylene, butadiene
10 Crude bitumen and butylene) and aromatics (benzene,
toluene and xylenes) through the
0 processes of steam cracking and catalytic
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec
naphtha reforming to produce
2007
petrochemical derivatives (monomers
and polymers).
Canadian tar sands also provide the
Figure 7 Historic pricing of Canadian crude oil potential for contributing some by-
products that could be used as
source crude oil is not nearly as valuable different ratios of feedstock to calculate petrochemical feedstocks. The process of
as benchmark crude oil. crack spread. Several of the more extracting bitumen from tar sands
Whether a refiner can be profitable or prominent ratios are: produces small quantities of light gases
not processing tar sand-derived crude oil — One barrel of crude oil producing (methane, ethane and propane) and
can be measured quantitatively using an one barrel of gasoline light liquids (butane, pentane and
industry standard called refinery crack — Three barrels of crude oil producing naphtha). The methane, if produced in
spread. Although different organisations two barrels of gasoline plus one barrel of sufficient quantity, could be steam
define the crack spread in similar but heating oil reformed to produce ammonia,
different ways, we present here refinery — Five barrels of crude oil producing methanol, carbon monoxide, hydrogen
crack spread as defined by the New York three barrels of gasoline plus two barrels and their derivatives. The C2-C6 fraction
Mercantile Exchange (NYME), which of heating oil. could be steam cracked to produce
publishes this data on a daily basis. The The calculated refinery crack spread olefins. The C6+ material could be
NYME calculates the refinery crack is used by options traders to buy (call catalytically reformed to produce
spread as the difference between the options or long call) or sell (put option aromatics.
sales price of a unit of refined fuels or short call) dry barrel contracts to Bitumen upgrading processes (delayed
gasoline (unleaded regular gasoline) and coking, gasification, hydrocracking and
heating oil (low sulphur heating oil) Densities of canadian crude oils hydroprocessing) produce the same
compared to the purchase price of the starting materials for producing
amount of light and sweet crude oil Bbl/mt petrochemicals. Syngas produced from
(benchmark crude oil) required to Heavy Canadian crude oil 6.9 gasification could also produce hydrogen,
produce the refined fuels. Light/Medium Canadian crude oil 7.3 ammonia, methanol, oxo-alcohols,
The NYME assumes in its calculation Canadian bitumen 6.2 Fischer-Tropsch liquids and their
that one barrel of crude oil produces one derivatives.
Using these conversion factors, Table 2 has
barrel of refined fuel. Although this is An indirect source of petrochemicals
been regraphed, as shown in Figure 7.
not precisely true, it serves as an easy feedstock could also be provided by
means for calculating refinery crack expanded Canadian tar sands
spread. Different organisations use Table 2 production. Tar sands upgrading

74 PTQ Q1 2009 www.eptq.com

 Tar sands industry
Syncrude’s 2007 cost of tar profitability In-situ 2007 cost of tar sands
sands production The Alberta tar sands industry has production
experienced extended periods of low or Cash costs of production 9.95
Bitumen mining costs
no profitability and recent periods of Natural gas purchases 9.95
Overburden removal 2.14
considerable profitability. The tar sands Depreciation & SGA costs 6.80
Bitumen production 9.90
production business is primarily a fixed- Sum bitumen production 26.70
Purchased energy 2.33
Sum bitumen production 14.37 cost business. A certain threshold crude
oil price provides adequate return on Husky upgrading costs
Upgrading costs investment, and prices above the Operating costs 8.95
Suncor in-situ bitumen costs
Processing costs 3.63 threshold provide considerable profit. Sum upgrading
Q407 8.95
Turnaround & catalyst costs 0.45 However, below the threshold price
Purchased energy 2.77 level, profits evaporate. Total cost of synthetic crude oil 35.65
Other & research 2.54 The early Suncor and Syncrude Net sales price 65.79
Sum upgrading 9.39 commercial projects were driven by Net operating costs 35.65
active Canadian government Transportation & selling (EnCana) 2.75
Total cost of synthetic crude oil 23.76 involvement, as were the high-risk Royalty payments 5.83
Net sales price 82.07 offshore production programmes off Net profit 21.56
Net operating costs 23.76 eastern Canada (Hibernia and White
Royalty payments 12.81 In-situ bitumen production costs 26.70
Rose). After the initial Suncor and
Net profit 45.50 Upgrading costs 8.95
Syncrude capital investments were
Transportation & selling (EnCana) 2.75
made, the tar sands industry remained Royalty payments 5.83
Mining costs 14.37 dormant for nearly 20 years.
Upgrading costs 9.39 Net profit 21.56
Those production facilities that have Net sales price 65.79
Royalty payments 12.81
been fully depreciated were making
Net profit 45.50
considerable profits, as are those that
Net sales price 82.07
were built prior to the 2005-plus run-up Table 4
in process industry capital costs. Whether
Table 3 current announced capacity will be built price for selling its crude at an average
on schedule, deferred or cancelled is a price of C$82.07. After subtracting the
requires H2, which is most often function primarily of the market price of previously described operating cost and
provided via the steam methane crude oil and the capital costs to build its royalty payments of C$12.81/bbl,
reforming of natural gas. Hence, Alberta the plants. Syncrude was able to realise a net profit
upgraders will attract natural gas The fragile nature of tar sands of C$45.50/bbl. This level of margin
pipeline supplies if the offering price is profitability was summarised in a describes in full the enormous
attractive compared to their alternative Financial Times article of 12 September emphasis in producing Canadian tar
source (gasification of delayed coke). 2008 during a period of rapidly falling sands in the current crude oil economic
Raw natural gas in Alberta as well as crude oil price declines: “Total’s extra environment.
other potential supply sources (proposed heavy oil sands project in Canada A similar economic environment was
MacKenzie Valley pipeline) is generally (Joslyn) requires an oil price of just experienced by in-situ (mostly steam-
rich in NGLs, which could economically below $90 a barrel to achieve a 12.5% assisted gravity drainage and cyclic
be extracted from wet natural gas to internal rate of return, while Total’s steam stimulation) producers of
produce additional quantities of developments in the deep waters off Canadian tar sands. To develop
petrochemicals. Angola need about $70 a barrel, the reasonably representative economics,
company revealed in a mid-year production cost data were combined
Market pricing of tar sands presentation.” from three separate in-situ producers
ERCB maintains a history of prices for PTQ reported that the cost of (Suncor, Husky and EnCana). The results
Canadian crude oils. These can be used producing bitumen from Canadian tar are presented in Table 4. Data for Suncor’s
to compare heavy and light conventional sands is $13.21/bbl, while the cost to Firebag SAGD bitumen production costs
crude oil prices with the corresponding upgrade the bitumen to light, sweet for Q4 2007 were C$26.70/bbl. During
prices for bitumen on a consistent synthetic crude oil is $15/bbl. According the same period, Husky Oil reported
basis. Figure 6 shows ERCB published to ENI Chairman Paolo Scaroni: average upgrader costs at its Lloyminister
monthly prices for Canadian crude oils “Personally, I expect oil prices will go facility of C$8.95/bbl. The sum of these
for 2007. further down. The limit is the cost of the is an averaged in-situ synthetic crude oil
These values have been converted to most expensive barrel of oil, which is cost of C$35.65/bbl. When transportation
US dollars on the basis of published the Canadian tar sands, which cost and selling costs (averaging C$2.75/bbl
currency translation prices (Wall Street $65–$70 a barrel. This seems to me the for EnCana) are added to representative
Journal, 24 July 2008) at 0.987 US$/C$. bottom. Otherwise, those supplies will royalty payments of C$.83/bbl, a net
The mass quantity has also been not be coming.” profit of C$21.56/bbl was realised when
converted from metric tonnes to barrels Oil Sands Review magazine quarterly an average netback sales price of C$65.70
using the density factors for Canadian summarises the economics of existing was attained.
crude oils shown in Table 2. tar sands production units in Canada.
What Figure 7 shows is that all of the Table 3 summarises the major cost
crude oils move directionally with global components for mining costs of
prices. Bitumen is priced at a slight Syncrude Canada during Q4 2007. The
discount to Canadian heavy crude oil cost for bitumen production was
(less than $1/bbl discount), while C$14.37/bbl, and the cost to upgrade
Canadian heavy crude oil is priced on the bitumen to synthetic crude oil was Tony Pavone is Senior Consultant
average at a $10/bbl discount to a C$9.39/bbl, for a total production cost with Stanford Research Institute (SRI)
mixture of conventional Canadian light of C$23.76/bbl. During Q4 2007, Consulting in San Francisco, California.
and medium crude oils. Syncrude was able to realise a netback Email: tpavone@sriconsulting.com

www.eptq.com PTQ Q1 2009 75

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 Beyond turnaround
planning
Utilising process- and unit-specific knowledge transfer to improve turnaround
execution. A better approach is needed to ensure the transfer of critical event
information to an experience- and discipline-diverse workforce

Brian Cormier Resource Development Company

Charles F Gillard C F Gillard and Associates

H
ow often is a plant’s year spoilt up P&IDs, blind lists, expandable Gantt thin to take time away from repairing
by poor performance on a charts and pages of procedure check-off process equipment. Event-specific
maintenance turnaround? sheets. Now what? training and awareness for contractors,
Excellent safety and environmental who will be brought in by the hundreds
performance, outstanding cost Executable knowledge transfer to support the field work, is often limited
management and near perfect reliability Herein lies the fundamental problem. to general refinery safety training and
— all hard earned through great effort — Unfortunately, the same zeal applied to tailgate job safety analyses (JSAs) during
can be destroyed by poor performance planning and scheduling is too often not shift change.
during a single turnaround. Turnarounds paid to transferring those critical details Yet, the probability of safely meeting
are almost always well planned. The to the minds of the personnel actually the turnaround event’s goals and
problem lies in executing that well- executing the work. Many work groups objectives so heavily depends on these
crafted plan. (including operations, technicians, groups working closely and effectively
Successful execution is dependent on contractors and vendors) are given a together. How can your refinery ensure
communication and information one- or two-day overview of big picture this complex co-ordination has the best
transfer from the planners to the doers. concepts such as critical path, a chance of happening and certify that
Moving from a traditional informal and shutdown/de-inventory strategy and a everyone has the knowledge they
unstructured approach to a knowledge general timeline of execution. This type require, both by craft and individual, to
engineered communication and of training is usually given in a group work safely and productively to meet
information exchange programme classroom setting about four to six weeks your turnaround schedule?
greatly decreases the risks, cost and prior to oil out, but regrettably provides
duration of turnarounds. A structured no verification that the necessary Communication is key
approach and detailed agenda for knowledge has been successfully The success of any turnaround can be
turnaround information exchange that transferred and can be applied when greatly improved, while reducing the
ensures success are imperative. executing the work list tasks. associated risks, simply by implementing
Maintenance turnarounds and process While the variability and lack of detail a rigorous, well-structured knowledge
unit revamps are arguably the greatest provided in such traditional training transfer system that communicates the
points of exposure for refineries in terms sessions have long been a concern, the proper process- and unit-specific
of safety incidents, production delays skilled workforce attrition that the information, specifications and
and lost profits. These events require a industry faces today magnifies the risks, procedures to all those involved. This
tremendous amount of planning, increases the need for best practices and means that all of the tasks, schedules,
awareness and motivation to ensure a calls for a new paradigm: process- and priorities, contingencies and perceived
safe and successful execution. unit-specific knowledge transfer. risks that should or might occur to a
Turnarounds are a time when the unit group of workers, who range widely in
is in a constant state of flux through Skilled workforce attrition terms of craft, experience and
shutdown, de-inventory, clearing and Senior plant operators are retiring in responsibility, need to be documented,
cleaning, mechanical work-over, unprecedented numbers, and with them structured and delivered to the
inventory and startup. The number of goes invaluable best practices, process appropriate audience through a
personnel supporting these activities knowledge and expertise. They are being validated process.
rises and falls in a typical bell curve-like replaced with new hires, each with a Conversely, miscommunication and
fashion. unique background and varying degrees misinformation typically lead to poor
Planning and scheduling activities of expertise and knowledge. Many have decision-making, which creates
begin months or even years in advance. never been through a unit turnaround misdirection and ultimately results in
Plans and contingencies are revised again before. Detailed process- and unit- confusion and potentially hazardous
and again with the help of operations specific knowledge transfer is needed situations. That confusion becomes
and maintenance staff, tenured to close the knowledge gap and contagious as shift changes take place
personnel, outside supporting vendors reduce risk. across all disciplines and can easily cause
and refining peers. Much time and effort Operations staff are becoming leaner a schedule delay of one or two days
is spent planning every conceivable because of this demographic change, before everyone can realign as a team
detail, with the single-minded goal of and time is often not available to and regain momentum.
performing the work safely and on operators for training activities outside The other vital part of a successful
schedule. The product of this effort is of their daily operating tasks. turnaround is the agreement on common
often a thick binder containing marked- Maintenance resources are stretched too goals and objectives by all the

www.eptq.com PTQ Q1 2009 77

www.ptqenquiry.com
for further information
 key objectives are duration and typical
scope
— Training on turnaround management
tools: this is training on the tools used
for managing the turnaround. For
example, training on how the blind list
is provided and how to use it
— Information on the specific
upcoming turnaround:
– Work schedule
– Organisational structure, such as
how the turnaround is going to be
staffed, work schedules and work
assignments
– Turnaround activities, such as
critical path and heavy lifts.

2. Project task tracking — critical path

schedule:
— Use of typical project task tracking
with the inclusion of anticipation of
discoveries and changes that may be
necessary during the actual shutdown.

3. Shutdown of the unit:

Figure 1 The RDC personalised learning path is part of the knowledge engineering — General step-wise overview of how
solution, enabling cost-effective transfer of job-, site-, and process-specific skills based this unit is shut down
on the individual employee’s role and existing skill set — More detailed procedure review of
unit shutdown by process system (ie,
departments involved. Nothing will kill practice and each turnaround will differ preheat train and pumparounds)
a turnaround faster than departments based on the backgrounds, expertise and
working independently toward their biases of the key players. More often 4. De-inventory and cleaning of process
own objectives. It takes many disciplines than not, planning styles will vary from piping/vessels:
working as a team to achieve a successful one planner to another and from one De-inventory:
turnaround, and only one group or turnaround to the next; formal — Understanding the difference in
department from the usual sectors of communication of the plan to all parties clearing process liquids vs gases
management, process engineers, involved tends to relax as the event — What utilities are available to
maintenance, operators, turnaround co- draws closer; and training is general in facilitate the clearing process (ie, flare
ordinators and contractors with nature, casual in format and varies based and oil recovery system) and what are
misaligned priorities can cause large upon the experience of the trainer. So, their operating capacities?
amounts of discourse, delays and costly you may have a good turnaround if you — How dead legs and trapped liquids
setbacks. For this reason, everyone must have the right people in leadership should be handled. What lessons have
agree on the primary target and process positions, or you may have a disastrous been learned from previous
of the turnaround to improve the turnaround without an established turnarounds?
chances of success and reduce risks. This knowledge transfer process in place. — Lessons learned might include:
can also best be achieved by transferring In order to be effective, a turnaround – A little bit of liquid hydrocarbon
and certifying the understanding of the training knowledge base should cover left in a low spot can really slow down a
goals, assignments and work details in the major strategic initiatives, from which turnaround while shift after shift is
order to create a cohesive, efficient and a consistent set of learning objectives can spent trying to pass the explosivity or
unidirectional team. Communication is be created and assigned. It should be hydrocarbon content test on a vent
the key. But with so many diverse groups dynamic in design, with the capability to – Drain and purge lines are usually
and talents, dissemination of information deliver a personalised learning path, small compared to normal process lines.
must be done in a way that is efficient tailoring the knowledge transferred based It is frequently difficult to get enough
and effective. upon the individual’s role as a contractor, flow through the gas purge inlet and
Refining companies would be prudent new hire operator or experienced outlet piping to carry liquid down a line
to take a much closer look at how they maintenance craftsman. In other words, and impossible to carry liquid up a
are effectively transferring that valuable you need to get the right information to vertical pipe run
knowledge across this spectrum of the right people — not all of the – Installation and use of big-bore
workers. Successful companies will information to all of the people — and steam lines at the discharge of product
ensure that a well-engineered, formal then you need to deliver the knowledge draw and pumparound pumps can help
knowledge transfer process is in place in a consistent and efficient process that to significantly reduce de-inventory
that certifies critical turnaround certifies full knowledge transfer to 100% times of those circuits and have the two-
information is documented, organised proficiency. fold effect of enhancing the cleaning
and communicated in the right quantity, Structuring the knowledge base in a process.
to the right individual and craft, and in modular fashion offers flexibility in Cleaning:
the context that is relevant to their role delivery of the information. The — Use of the best-in-class cleaning
and responsibility. following are the recommended key technology. Liquid circulation can be
modules and associated learning costly in terms of waste effluent
Consistency objectives: processing and the equipment and real
Without a rigorous process and system 1. Turnaround basics: estate to facilitate the process. Vapour-
for knowledge transfer, there is no best — General overview of a turnaround: phase technology is proving to be more

www.eptq.com PTQ Q1 2009 79

 efficiency

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www.ptqenquiry.com
for further information
effective in terms of cleanliness and can enormous pile of relevant data and heightened awareness and culpability,
be coupled with the unit steam-out organise it into a useful knowledge base. dictating that refining companies can
process A well-structured turnaround no longer continue to use a broad-stroke
— Illustration and proper document- knowledgebase template is now available approach to training and knowledge
ation of isolation, blinding and cleaning that is modularised in the format certification. Group training in a
of specific vessels and equipment. previously referenced and through a classroom setting for contractors,
proprietary Knowledge Engineering especially when they are talked through
5. Safety, work permits, tagging and process, made site-, unit- and event- the training, watch a video or two and
blinding: specific for each unique plant. then complete a paper test, can leave a
— Appropriate training for employees Throughout the instructional design refinery exposed in the wake of a deadly
and contractors of permitting process process, RDC works in partnership with accident or explosion.
— Review of hot work and vessel entry refining companies to blend information Workers must be remediated and
permits from existing turnaround plans into this certified to prove 100% competency
— Review of tagging and blinding learning tool. In addition, interviews are across all knowledge requirements to
system. conducted with the most experienced perform a job safely. The technology is
planners, operators and maintenance available to pre-assess a worker’s existing
6. Work list execution: personnel to gather best practices knowledge gaps with respect to a group
— Proper material, crafts and access to information that can be cultivated into of learning objectives, automatically
complete specific turnaround tasks knowledge, tied to learning objectives deliver a personalised learning path,
— Teams for inspection, verification and overlaid in a craft- and unit-specific and post-assess and validate proficiency
and sign-off of completion of each task manner. until all knowledge gaps are
— Documentation and tracking system It is important to clarify that the remediated.
to ensure managers know of work status instructional design focus should be on
and can quickly update any critical path adult learning and conveying technical Conclusion
assessments based upon discovery process knowledge. As adults, we absorb Successful and lower risk turnarounds
work. knowledge differently than we did in can be achieved by establishing a best
our younger years. Adults require practice for documenting, organising
7. Unit start-up: participation throughout the learning and disseminating information. Skilled
— Review of overall start-up process process and the information that is workforce attrition is a subject that is
— Step-wise review of start-up by being presented must be relevant to the tirelessly discussed in the energy
process system. learner’s specific job responsibilities and, industry, as well as much of
to a greater extent, be information that manufacturing. Every refining company
8. MOC process: fills gaps in their knowledge. One-size- invests a hefty sum in the professional
— Proper orientation of management fits-all training in a classroom setting development of its workforce. An
of change (MOC) process for change largely has proved ineffective at operator, through training efforts and
and approval of work plan, document- efficiently transferring such detailed on-the-job experience, develops a wealth
ation and equipment repairs technical knowledge. of best practices knowledge over a 25-
— Beneficial for documenting actual year career.
turnaround events and updating Differential learning We encourage you to retain your
information for use after turnaround. Crafting a complete and customised company’s investment by proactively
knowledge base is only half of the total capturing that knowledge and imparting
Keep best practices evergreen solution. Automated delivery of this that wisdom to the incoming generation
The adage that, if we do not learn from information to the learner and an of operators. Work with an instructional
the past, history is bound to repeat itself assessment process that validates the design leader in the industry who
rings especially true for turnarounds learner has absorbed and comprehends provides the knowledge engineering
given the typical five- to seven-year the information completes the closed- and differential learning tools to cost-
interval between events and the loop solution. effectively capture, retain, access and
continued loss of experienced refining The learning environment is capable transfer the process-, job-, event- and
personnel to retirement. of handling the flux of hundreds of unit-specific knowledge needed to
Any turnaround training knowledge workers that will support a given improve ongoing operating margins.
base must be kept evergreen. Most turnaround event. Access to the
refineries conduct post-event reviews to turnaround knowledge base content is
identify and document lessons learnt personalised, based on the role(s) an
and areas for improvement. Those individual is assigned. The scope and
enhancements are often made to the depth of a curriculum assigned to a Brian Cormier is Director of Oil and
planning book, only to be shelved for contractor supporting the turnaround Gas Solutions for Resource Development
the next turnaround and forgotten or will differ from that of a unit operator, Company (RDC) and is based in Houston,
overlooked in the next turnaround because the learning environment Texas. He has ten years of refining industry
cycle. That valuable information came personalises each individual’s learning experience in supporting turnaround
at a significant price, be it sweat equity path, based upon their role and the prior activities. Cormier holds a BS in
or otherwise, so make the effort to build level of knowledge they exhibit. Training environmental science from Sam Houston
it into additional learning objectives. on the unit’s permitting process, as well State University.
as who is qualified to sign a work permit, Email: bcormier@resourcedev.com
Knowledge engineering can easily be applied to the learner’s Charles F Gillard is President and CEO,
solution knowledge requirements by assigning a C F Gillard and Associates. He was
The good news is that refineries do not permit-qualified role to a maintenance previously with Shell Oil Company for
want for information. Volumes of P&IDs, contractor, cleaning vendor or operator. 35 years in a variety of operations,
procedures, Gantt charts and blind lists engineering and information technology
reside in binders created for previous Knowledge gaps = risk positions. Gillard has a BS in chemical
turnarounds. On the surface, it seems an Accidents and safety impacts associated engineering from Purdue University.
almost impossible task to take this with turnarounds in recent years have Email: charlesgillard@cfgillard.com

www.eptq.com PTQ Q1 2009 81

www.ptqenquiry.com
for further information
 Improving VGO
hydrotreater operation
A practical, industrial data-derived tool can give refiners confidence in simulating the
actual benefits of additional hydrogen for improved VGO hydrotreater performance.
A lumped parameter dynamic simulation modelling approach is employed

Darius Remesat
Koch-Glitsch Canada

A
lumped parameter dynamic public domain dynamic hydrotreater pressure, temperature, hydrogen-to-oil
model, using both Microsoft Excel research is based on pilot plant data ratio)
and AspenTech HYSYS software, that do not translate well to industrial — Is run in dynamic mode to track the
for industrial refinery/upgrader vacuum applications. A key element of this key variable product sulphur and the
gas oil (VGO) hydrotreaters has been tool’s development entailed gathering a representative value of performance
developed from proprietary and public substantial amount of relevant weighted average bed temperature
steady-state hydrotreater models. The industrial data (14 operating industrial (WABT)
model is based on industrial plant data VGO units, with permission to publish — Incorporates familiar software (Excel
and tracks changes in intrinsic reaction data from six operators) specific to and HYSYS) for easy translation into
rates based on catalyst deactivation, VGO hydrotreaters. existing operations and acceptance by
wetting efficiency, feed properties and users
operating conditions to provide useful Methods and materials — Is correlation based, demonstrating
information, such as required operating The VGO hydrotreater model semi-predictive tendencies
temperature, outlet sulphur composition developed: — Is used to represent a trickle fixed-
and chemical hydrogen consumed. — Uses lumped parameters that match bed reactor in operation.
The model credibly simulates local data available from industrial
disturbances and represents the three operations Data gathered
distinct operating zones during the — Uses a mix of industrial correlations, Detailed industrial VGO hydrotreater
hydrotreater run length: start-of-run kinetic theory and academic research data, under confidentiality agreement,
(SOR), middle-of-run (MOR) and end- findings were obtained and used from six
of-run (EOR). This correlative, partially — Factors in changes in operating operators. In addition, data from
predictive model can be applied to conditions in response to disturbances eight other plants was used in
demonstrate the tangible economic in operation testing the developed model. Catalyst,
benefits of increasing hydrogen use to — Incorporates changing reaction rate, process and laboratory data, plus
improve the operation of a hydrotreater wetting efficiency, catalyst deactivation equipment information were among the
by increasing run length and/or in the three zones of the hydrotreater needed and gathered data. Table 1
improving crude processing. run life (ie, SOR, MOR and EOR) provides a sample of the information
— Uses parameters for all key process gathered from the industrial operating
Hydrotreating developments variables (sulphur, hydrogen partial units.
Hydroprocessing has become a key
refiner/upgrader operation due to two
key developments. First, transportation Catalyst/reactor information gathered from six industrial plants
regulations for refined products have Unit Plant A Plant B Plant C Plant D Plant E Plant F
evolved to significantly reduce the Reactor diameter, ft 13 12 12.5 12 11 14
maximum amount of sulphur allowed Catalyst type NiMo NiMo CoMo NiMo NiMo CoMo
(eg, <30 ppm gasoline in North America on Al on Al on Al on Al on Al on Al
and <10 ppm diesel in Europe). Second, Catalyst volume, ft3 4424 2865 5926 6523 2415 4189
it is becoming necessary for refiners to Catalyst weight, lb 207 928 110 016 266 650 316 650 128 478 163 371
process heavier, more sour crudes due to
reduced availability of sweeter (low Catalyst density, lb/ft3 47.00 38.40 45.00 48.54 53.20 39.00
sulphur) crudes. As a consequence, there Cycle length, years 2.60 2.00 1.80 1.08 3.00 2.28
is a need to remove more sulphur than Reaction type HDS HDS HDS HDS HDS HDS
previously required. Desired product S, wt% 0.04 0.05 0.03 0.03 0.04 0.04
Unfortunately, refiners/upgraders Typical feed S, wt% 1.70 0.80 1.50 2.20 1.40 0.90
rarely achieve their run lengths and
crude throughput objectives for VGO SOR average temp, °F 605 590 660 580 631 610
hydrotreaters. 1 The performance Typical LHSV, Hr-1 0.76 1.23 0.54 0.41 0.88 1.63
shortfall is mostly due to disturbances Feed type LGO LGO LGO LGO LGO LGO
Suggested reaction order 1.65 1.50 1.60 1.70 1.55 1.40
(crude flow, feed compositional,
Activation energy, cal/mole 27 000 29 000 32 000 24 500 26 500 27 500
sulphur, metals, and/or hydrogen
partial pressure changes) that reduce
the effectiveness of the catalysts. Most Table 1

www.eptq.com PTQ Q1 2009 83

 DBT hydrogenation route to represent
the overall sulphur conversion, treating
100 all the sulphur as DBT should provide a
representative conversion of all the
90
sulphur. All the sulphur species that are
80 easier to convert than DBT will be
considered totally converted and lumped
Ref 5 model
70 into the amount of DBT converted. The
reversible dehydrogenation portion of
Cat alyst ac t ivit y, %

60 this reaction provides a realistic

representation of the reduced driving
50 Thesis model force of hydrodesulphurisation at higher
40 temperatures.2

30 Catalyst deactivation
Ref 20 model A crucial step in developing an accurate
20 hydrotreater model is developing a
realistic representation of catalyst
10
deactivation and including it in the
0 reaction rate expression (ki), illustrated
18/4/0 7/6/05 27/7/05 15/9/05 4/11/05 24/12/05 12/2/06 3/4/06 23/5/06 in Equation 1. Overall, 30 correlations3
Date were modified or developed to provide
the khds in Equation 1.
Instead of using classical
Figure 1 Catalyst activity profiles generated from various models evaluated representations (eg, Thiele modulus) for
incorporating catalyst deactivation using Plant D data the S-shaped catalyst deactivation curve,
operator steady-state correlations were
1
Dynamic approach used as a starting point, since they
_b b i
p g 1-2ηei
provided a match to the type of data
Spi = *khds (i-1)
to industrial 1 e Ti-1 Ti f Pi-1p fGi-1p + 1 4
LHSVi Pi Gi S2η ei -1 available from the operating units.
hydrotreater kinetics fi
(1) Figure 1 illustrates various representative
To dynamically track catalyst behaviour catalyst activity models, using Plant D
by calculating outlet sulphur In reviewing plant performance, data, considered for use in this research.
composition from known or observed pressure (P) and gas-to-oil ratio (G) were The Reference 20 line based on publicly
results of an industrial hydrotreater, the included in Equation 1, along with their available literature has a very steep SOR
key product variable (Sp) was created in respective exponential factors (p and g) and exhibits a classical S-shaped curve
the form of Equation 1. The model to better model the operation. Note that for catalyst deactivation, predicting EOR
involving Equation 1 takes into account the variables P and G are key contributors prematurely.4 The Reference 5 line is
process data, including temperature (T) to hydrogen effectiveness in the from an industrially focused consultant.1
and liquid hourly space velocity (LHSV) hydrotreating reaction. There appears to be a factor for SOR
available from the plant data-gathering To address the lumped sulphur deactivation, but the remainder of the
system; determines the impact of composition provided from the curve is essentially a negatively sloped
internal and external mass transfer industrial units, dibenzothiophene straight line.
resistance in a lumped parameter (DBT) was chosen as the sulphur It was apparent that no previously
evaluation (ηe); and provides a component on which to base the overall developed publicly available or steady-
relationship for catalyst deactivation sulphur reaction kinetics. It is state catalyst activity correlation would
embedded in the reaction rate expression hypothesised that by using the slower match the industrial data gathered and
khds: thus meet the objective of this research.
Enhancements to the base MOR
Average calculated parameters for sulphur product composition correlations were made to better
represent SOR and EOR catalyst
Plant Average p Average g Average b, °F API SOR Viscosity, SSU @ 100°F deactivation in a VGO hydrotreater.
A 0.46 0.50 21 500 30.1 58 Variables (eg, metals, olefinic content,
B 0.63 0.54 23 700 27.3 478 aromatic content, temperature, hydrogen
C 0.51 0.64 23 350 19.5 453 partial pressure, hydrogen-to-oil ratio,
D 0.89 0.53 23 100 27 243 LHSV, sulphur content, nitrogen content,
E 0.38 0.47 21 700 30.8 46
H2S formation, aromatic saturation and
F 0.39 0.55 24 700 25.8 1525
API) that should be impacting catalyst
deactivation in the SOR and EOR regions
R 0.41 0.51 24 400 29.2 1310
were evaluated and input into a dynamic-
S 0.59 0.63 23 270 20 430
T 0.36 0.53 23 000 26.7 300 based format that resembled catalyst
U 0.53 0.59 24 000 23 1000 vendor steady-state correlation formats.
W 0.44 0.56 24 000 25 900 The catalyst activity profile from this
X 0.38 0.60 24 600 22.3 1650 tool is included in Figure 1 for comparison
Y 0.37 0.52 23 400 28 500 purposes. This model appears to capture
Z 0.78 0.63 24 600 21 1568 and represent disturbances in the reactor
more accurately than any other models
Plants A-F, full data sets published; plants R-Z, data in this table is permitted to be published. evaluated.

Model particulars
Table 2 For the outlet sulphur composition from

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for further information
the VGO trickle bed hydrotreater,
represented as Equation 1, the parameters Statistical results for sulphur and WABT from each plant studied,
b (temperature), p and g were tested with model vs plant
the operating data from all 14 plants to Plant A Plant B Plant C Plant D Plant E Plant F
determine a feasible way to represent Sulphur R2 0.86 0.92 0.90 0.93 0.95 0.88
these parameters for each VGO WABT R2 0.91 0.925 0.925 0.927 0.935 0.916
hydrotreater. Table 2 shows the final
parameter values used for the 14 plants
from which significant data were Table 3
obtained (six plants allowed detailed
publishing of the results). The parameters
were evaluated separately with the data
sets and then together to check for
cross-correlation between the parameters. 600
The parameters were adjusted during
the simulation run for each plant.
Equation 2 provides a calculation to 500
determine parameter p, based on
hydrogen partial pressure (PH2, psig) and Plant
lumped mass transfer variable (ηe). Both
Out let sulp hur, p p m
400
of these variables are crucial in converting
sulphur in the hydrotreater, and thus are
incorporated in the calculation for 300
parameter p:
Sim ver 9
p = _ PH2
ieηe (2) 200
4500

Equation 2 was based on a steady- 100

state catalyst vendor correlation for this
parameter in VGO hydrotreater service.
The wetting efficiency factor was 0
included (ηe), since the overall reaction 17/2/05 25/10/05 2/7/06
relies on reactants contacting the catalyst Days on-line
for the reaction to proceed. A reduction
in contact will reduce the impact of any
hydrogen partial pressure benefits. Figure 2 Plant D: product sulphur composition, model vs plant data
For the temperature factor b, there
appears to be a relationship to the applications. The sulphur product predictions to the plant data.
crude’s viscosity (µ). The viscosity at specification for the VGO hydrotreaters For the product sulphur, the model
SOR for each crude is included in Table studied was in the range of 300–500 showed a R2 of approximately 0.86–0.88
2. A logarithmic relationship, with an R2 wppm, well above the ULS specifications for two plants (A and F) and over 0.90
of 0.978 for the 14 plant data set (R2 of of less than 10 wppm. for the other four plants. For the WABT,
0.980 for the six plants published in this the model had an R2 in the range of
study), has been fit, resulting in Plant results — 0.91–0.935. Overall, the model provides
Equation 3: entire run length a credible match of the overall plant
The model output provides the WABT operation, especially considering that
b = 866.24Ln (µ) + 18162 (3) and sulphur outlet product, both the model uses a lumped parameter
variables that are constantly measured at approach and there are inaccuracies in
Equation 4, for parameter g, hydrogen- industrial operations. The sulphur in the the measurements and operator choices
to-oil ratio, appears to be linearly related product is the primary specification for (on temperature), which as shown are
to the API of the crude (ie, the more the VGO hydrotreater, while the reactor not always the best method of mitigating
dense the crude, the larger the required temperature is directly related to the a disturbance.
hydrogen-to-oil ratio). Typically, more catalyst activity (as catalyst activity goes
hydrogen is needed for hydrotreating down, reactor temperature goes up). The Plant D sulphur and
heavier crude, since these types of WABT of the reactor is plotted over time, WABT results
sulphur molecules are embedded in the which is a key variable the operators use Plant D operated its VGO hydrotreater
heavier crude molecules and more to control product sulphur. This for one year and four and a half months,
hydrogen is required.4,5 As a result, the temperature is an indirect indicator of well below the desired run length of
relationship between hydrogen-to-oil catalyst deactivation. As catalyst activity four years. The results of the model
ratio and API (crude specific gravity) is decreases (from coking, fouling or predictions, shown in Figure 2, for the
appropriate. The linear relationship plugging), the reactor temperature is product sulphur concentration were an
between parameter g and the API gravity typically raised to try to increase the R2 of 0.93 for the product sulphur.
of the crude feed can be described by activity of the remaining active catalyst Between 20–130 ppm, the model better
Equation 4 (R2 of 0.9854 from 14 (prior to the need to reduce crude flow to matched the data with an R2 of 0.957.
plants): the reactor). For less than 20 ppm, the R2 was 0.85,
Data for six plants were compared to while above 130 ppm the R2 was 0.895.
g = -0.0141API + 0.9146 (4) model predictions for the plant WABT The model was not as effective in
and product sulphur composition. Table capturing the spikes above 130 and
This linear relation (Equation 4) does 3 provides a summary of the statistical below 20 ppm. The lumped approach in
not apply to ultra-low sulphur (ULS) analysis used to compare the model the model and the inaccuracy in the lab

www.eptq.com PTQ Q1 2009 87

 samples at the extreme points are likely
contributors to the increased deviation
by the model outside the 20–130 ppm
680 range.
670 Figure 3 shows how the model WABT
660 predictions compared to the Plant D
data. The R2 of 0.927 indicates a very
650
WAB T t em p erat ure, oF

good model prediction given the lumped

640 approach, quality of industrial-scale
630 plant data and operator error
Plant D contributing to the inaccuracies in the
620
model. The model captures the operating
610
Sim ver 9 trends (changes in crude flow and
600 contaminants in feed) and thus provides
590 an insight into catalyst deactivation
580
during the entire run length. This newly
available information can be used to
570
17/2/05 8/4/05 28/5/05 17/7/05 5/8/05 25/10/05 14/12/05 2/2/06 24/3/06 13/5/06 2/7/06
determine ways to mitigate the impact
Days on-line of catalyst deactivation.

Catalyst activity
Catalyst activity is directly related to the
WABT, so WABT is a primary, easily
Figure 3 Plant D: WABT, model vs plant data attainable, yet indirect variable for
operations to control catalyst activity or
the rate of deactivation. Analysis of the
catalyst activity profile is helpful in
deciding when to schedule a unit
100 shutdown and how to mitigate further
deactivation. Figure 4 shows the catalyst
90 activity/deactivation profile for Plant D
from the model. This figure shows clearly
80
the impact of the disturbances during
70 the life of the catalyst. At disturbance 1,
7.5% activity decrease from a rapid increase in sulphur causes a 7.5%
Catalyst activity, %

disturbance 1 – Sulphur in feed up

60 reduction in catalyst life. If this impact
can be mitigated during the disturbance,
50
catalyst life can be extended. The two
40 disturbances noted in Figure 4 reduce
3% activity decrease from catalyst life by 10.5%, or four months.
30 disturbance 2 – Sulphur in feed up This information can be critical in
deciding what steps operations can take
20
to improve the performance or prepare
10 for a shutdown.
0
18/4/05 7/6/05 27/7/05 15/9/05 4/11/05 24/12/05 12/2/06 3/4/06 23/5/06
Predictability of developed
Date correlative model
The developed model in this research is
correlative. An exercise was performed
Figure 4 Plant D: catalyst deactivation from model to determine if the model could also be
considered partially predictive. A new
data set was obtained from Plant D,
which had a different catalyst (updated
Performance comparison between the two data sets for Plant D
version of existing catalyst) and a
Plant D: base Plant D: new run different starting temperature. The
Time started Apr 05 Nov 06 parameter correlations developed from
Time ended Jul 06 ? the entire sets of plant data obtained
T start,°F 580 602 were used. The model was able to deal
T end,°F 670 ? with a different catalyst and starting
R2 sulphur 0.917 0.927 temperature while using the same model
R2 temperature 0.916 0.934 parameters from a different data set to
SOR range, °F 580–630 602–655 obtain a representative and semi-
SOR T delta, °F 50 53 predictive evaluation of the operation.
Catalyst type Version 7 Version 8b The key point of this evaluation is that
Viscosity, SSU-100°F 243 243 the model calculations do not rely on
API SOR 27 27.1 any correlative analysis with this data
Parameter b, average 23 000 23 000 set. Table 4 compares the performance
Parameter p, average 0.9 0.92
of the model with the base Plant D data
Parameter g, average 0.54 0.54
and the new plant data.
Based on the catalyst activity profile
Table 4 to date, the model predicts a run length

88 PTQ Q1 2009 www.eptq.com

of 2.4 years, just short of the three-year
design rate, but more than double the Value of increasing H2 purity via increased crude throughput
previous data set of 1.08 years.
Plant Avg % H2 H2 flow, Avg crude, Avg crude $MM for $MM/yr
mmscfd kbpd increase, entire run over run
Application of the model kbpd length length
The developed model provides a valuable A 83 33 15.8 2.5 33.7 13.0
software tool that can be used by B 77 21 13.5 3.2 45.3 22.6
operators to understand the impact of C 76 28 14.4 2.2 20.3 11.3
changing a key process variable on the D 88 35 13.1 2.5 13.5 12.5
overall economics of the VGO E 86 23 11.3 1.5 20.0 6.7
hydrotreater operation. Operators can F 91 48.6 26.5 3.6 39.9 17.5
feel more comfortable justifying a
process change to improve VGO
hydrotreater performance (eg, Table 5
throughput), since the model is based
on industrial data and can track
disturbances and the overall performance Comparing increasing recycle pressure vs increasing H2 purity
of the reactor. Table 5 shows a summary
Existing reactor Model - 99% H2 Model - P up 15%
of the economic benefits that can occur
Plant Pressure, PH2, PH2, Avg crude PH2, Avg crude
by using increased hydrogen purity at psig psig psig increase, psig increase,
the same hydrogen flow rate (and thus kbpd kbpd
higher hydrogen partial pressure) for all A 675 560.3 668.3 2.5 644.3 1.2
six plants. B 1065 820.1 1054.4 3.2 943.1 1.7
For the value calculation in Table 5, C 970 737.2 960.3 2.2 847.8 1.2
an average price of $8.84/kscf for 99% D 1550 1364.0 1534.5 2.5 1568.6 1.1
hydrogen and a $25/bbl crude upgrade E 460 395.6 455.4 1.5 454.9 0.7
value was used. The additional crude F 475 432.3 470.3 3.6 497.1 1.6
that could be processed ranged from an
average of 1.5–3.6 kbpd, with the value
(revenue from added crude production Table 6
— cost of 99% pure hydrogen from a
third party) for each plant ranging from use and have confidence to introduce — As a decision-making tool based on
$13.5–45.3MM CAD over the run length the concept of increased hydrogen process variable changes
for each plant (or $6.7–22.6MM per (purity and thus partial pressure) to — As a training and learning tool to
year). improve hydrotreater operation. A gain operating experience
Refiners/upgraders can also increase representative dynamic model for — As a troubleshooting tool to identify
recycle pressure and thus reactor pressure industrial refiner y/upgrader faulty measurements, thus aiding
to boost hydrogen partial pressure and hydrotreaters has been developed based operators in operating the hydrotreater
improve catalyst performance. A booster on 14 actual operating hydrotreaters more effectively.
compressor is typically added to the (six of which can be published). The
recycle circuit. The model can be used to model accurately simulates local
make a comparison between raising disturbances and performs well over References
1 Robinson P, Catalyst life management with
hydrogen partial pressure via increased the entire run length of the hydrotreater a predictive deactivation model, NPRA
reactor pressure and raising hydrogen by competently representing the actual Plant Automation And Decision Support
partial pressure via increased hydrogen catalyst deactivation and incorporating Conference, San Antonio, 2004.
2 Kokayeff P, Aromatics saturation over
purity. This is an important analysis in a wetting efficiency factor to handle hydrotreating catalysts: reactivity and
determining which route, if any, to take mass transfer resistances. This robust susceptibility to poisons, Catalytic
to improve VGO hydrotreater model can be applied to demonstrate Hydroprocessing of Petroleum and Distillates,
1993, 14, 253–278.
performance. Table 6 shows the results the tangible economic benefit of 3 Remesat D, Improved vacuum gas oil
of increasing hydrogen purity (from increasing hydrogen (purity and flow) hydrotreating operation via a lumped
Table 5) to 99% if the recycle pressure is use to improve the operation of a parameter dynamic simulation modeling
increased by 15%. The increased recycle hydrotreater by increasing run length approach, PHD dissertation, University of
Calgary, May 2007.
pressure creates an increase in catalyst and/or improving crude processing. 4 Chao Y, Liaw H, Huang H, A mathematical
activity, resulting in an average rise of The model can also be used: model for the catalyst deactivation in a
crude flow of 0.7–1.7 kbpd. commercial residue hydrodesulfurization
reactor system, Chemical Engineering
The rise in crude flow from increased Communications, 1991, 104, 267–290.
recycle pressure is 43–54% of the rise in “The developed model 5 Smith M J, Chemical Engineering Kinetics,
crude flow from increased hydrogen Third Edition, 1981, McGraw-Hill, 7, 133–
purity. The impact of increased hydrogen provides a valuable 147.
6 Ho T, Hydroprocessing kinetics for oil
purity in the developed model translates
software tool that can fractions, Hydrotreatment and Hydrocracking
of Oil Fractions, 1999, Elsevier Science, 179–
into a more effective way of mitigating
catalyst deactivation versus simply be used by operators to 186.

raising the reactor pressure.6

understand the impact of
Conclusions changing a key process Darius Remesat, PhD, MBA, PEng is
By using industrial data for validation a Process Consultant and Business
purposes, and creating a model that
variable on the overall Development Director for Koch-Glitsch
responds to various disturbances during economics of the VGO Canada. This article is based on his
the entire hydrotreater operation, completed PhD work at the University
refiners/upgraders will now have the
hydrotreater operation” of Calgary.
necessary software tool to justify the Email: darius.remesat@kochglitsch.com

www.eptq.com PTQ Q1 2009 89

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 Clean diesel
hydrotreating
Design considerations for clean diesel hydrotreating. Critical issues are
discussed when designing a hydrotreating facility to produce diesel fuel
with very low levels of total sulphur

Ed Palmer, Stan Polcar and Anne Wong

Mustang Engineering

F
or over three decades, refiners sulphur compounds. Sterically hindered — Feed characteristics and variability
worldwide have been implementing dibenzothiophenes are a group of — Other product quality requirements,
various projects in their facilities to aromatic sulphur compounds that are especially cetane index
accommodate a variety of regulations to among the most difficult to remove — Catalysts selection
improve the quality of transportation when hydrotreating to very low sulphur — Optimisation of reactor process
fuels in order to reduce vehicle emissions. levels. This is particularly true for diesel variables
One of the key areas of interest has been fuels that contain significant quantities — Equipment design requirements
the reduction of sulphur in diesel fuel to of cracked stocks, such as FCC light — Reliability
very low levels. For example, since mid- cycle oil (LCO), which contains a large — Minimising product contamination
2006, the maximum sulphur content of concentration of aromatic sulphur — Handling of off-spec diesel product.
on-road diesel fuel in the US has been compounds. The effective removal of All of these factors should be carefully
limited to 15 wppm. Similar regulations these species requires tailored catalysts considered during the front-end
are in place or are in various phases of and process conditions, as well as process design.
implementation in many countries. consideration of other factors such as
feed nitrogen content and aromatics Process flow
Design considerations equilibrium. Figure 1 shows a simplified process flow
Middle distillates contain various types There are numerous issues to be diagram for a diesel hydrotreater. Fresh
of sulphur species, including mercaptans, addressed in the design of a hydrotreater, feed from the surge drum is heated with
sulphides, thiophenes and aromatic including: stripper bottoms, then mixed with

M. U. H2

Recycle M. U. H2
compressor compression

LCO Reactor
Feed
heater
SR diesel

Quench

Feed Amine
treating

ULSD product

Gas to fuel

CHPS
Sour water
HHPS

Sour naphtha

Steam Wash water

Sour water

Figure 1 ULSD hydrotreater HHPS/CHPS

www.eptq.com PTQ Q1 2009 91

 Reaction process variables
Maximum operating pressures for 321 SS and 347 SS stainless steel The key reaction process variables are:
— Space velocity
600lb flanges 900lb flanges 1500lb flanges
— Hydrogen partial pressure
321 SS 347 SS 321 SS 347 SS 321 SS 347 SS
— Make-up hydrogen purity
600°F 975 1030 1460 1550 2435 2580
— Ratio of total hydrogen to reactor/
650°F 950 1015 1425 1520 2375 2530
700°F 930 995 1395 1490 2330 2485 chemical hydrogen consumption
750°F 915 985 1375 1475 2290 2460 — Cycle length
800°F 900 975 1355 1460 2255 2435 — Reactor temperature.
850°F 895 970 1340 1455 2230 2425 For feeds that have a significant
aromatics and/or nitrogen content, a
nickel-moly (Ni/Mo) or nickel promoted
Table 1 cobalt-moly (Co/Mo) catalyst will be
used, along with an appropriate selection
recycle hydrogen. The combined feed is Nitrogen has to be removed to essentially of graded catalysts in the top of the bed
further heated by reactor effluent, then the same level as sulphur to reach the to mitigate reactor pressure build-up.
brought to reactor inlet temperature in ultra-low target. This means the catalyst For a given cycle length and treating
the charge heater. Reactor inter bed employed and the hydrogen partial severity reactor space velocity, hydrogen
quench may be required in one or more pressure selected must be consistent treat gas quantity and hydrogen partial
locations, depending on the volume of with a high nitrogen removal operation. pressure are the variables that are
cracked stocks (FCC LCO, light coker gas Normally, the bulk of the feed nitrogen optimised during the process design
oil) in the feed. This flow diagram shows is contained in light coker gas oil and along with reactor temperature. As the
recycle gas being used as quench. Reactor FCC LCO. The aromatics content of the hydrogen partial pressure is increased,
effluent exchanges heat with the feed will govern the chemical hydrogen the catalyst deactivation rate is reduced.
combined feed and flows to the hot, consumption at the low space velocities Thus, the space velocity can be increased
high-pressure separator (HHPS). Vapours and high hydrogen partial pressures accordingly for a constant cycle length.
from the HHPS are used to heat recycle required for very low sulphur diesel However, this is at the expense of higher
gas and stripper charge before being production. hydrogen consumption. Another
cooled in the reactor effluent air cooler Generally, cracked stocks can be important variable is the ratio of total
(REAC) and entering the cold, high- included in the feed up to the level hydrogen supplied to the reactor bed to
pressure separator (CHPS). Wash water is limited by the product cetane index or the chemical hydrogen consumption for
injected upstream of the REAC to remove gravity without having a significant that bed. This value should be between
ammonium bisulphide. HHPS liquid is impact on hydrotreater design. There is five and six for feeds with significant
combined with heated CHPS liquid and a small increase in the gravity and quantities of cracked stocks. This ratio is
flow to the product stripper. cetane index during the hydrotreating normally a “fall-out” number during the
Vapours from the CHPS are contacted reaction. If a significant improvement in process design, but there are instances
with amine in a scrubber for hydrogen cetane (say, three to five units or more) where it can control the design hydrogen
sulphide removal and flow to the recycle or gravity is required, a multi-stage circulation rate, particularly for cases
compressor suction drum. Make-up design using aromatics saturation where high purity make-up hydrogen is
hydrogen is compressed and combines catalysts in the second stage may be the used exclusively.
with the recycle gas in the suction drum. more economical option. The final From a practical viewpoint, one should
Some of the recycle gas may be purged choice will be driven by the magnitude be aware of the limiting pressure of the
from the compressor suction drum to of the improvement in gravity and alloy piping flanges in the reactor section
improve the purity of the recycle gas cetane required. when setting the hydrogen partial
hydrogen. If needed, the quantity will Obviously, the design product sulphur pressure and total operating pressure.
depend on the reactor hydrogen partial target is a key issue, not only from a This includes piping from the combined
pressure requirements and the purity of process design standpoint, but also for feed exchangers to the feed heater, from
the make-up hydrogen. off-site storage and transfer. For the the heater to the reactor, and from the
In the product stripper, superheated ultra-low sulphur diesel (ULSD) reactor to the combined feed exchangers
steam is introduced into the bottom of programme in the US, most new and (especially when the feed contains
the tower to effect the removal of revamp facilities have been designed significant quantities of cracked stocks).
hydrogen sulphide. Stripper overhead for a product sulphur content of 8–10 This piping will be a 300 series stainless
vapours are condensed and flow to the wppm to ensure a final product sulphur steel, and for 600 psi ANSI flanges this
stripper accumulator. Accumulator content of 15 wppm at the point corresponds to a maximum operating
vapour and liquid (wild naphtha) are of sale. pressure of around 800 psig at the reactor
processed in other off-site facilities. The Pilot testing of the feed is practically inlet when using 321 SS (Table 1) and 880
stripped diesel product is used to heat mandatory to confirm reaction process psig when using 347 SS. For 900 psig
the feed, it is cooled, then it flows to conditions. Testing for variations in feed flanges, the reactor operating pressure
drying facilities (not shown). This could characteristics, especially FCC LCO and can be increased to about 1200 psig
be a coalescer/salt dryer or a vacuum coker light gas oil back-end distillation, when using 321 SS and 1300 psig when
drying system. should also be considered, because the using 347 SS. This takes into consideration
separation achieved in the products pressures during relieving conditions.
Feed and product fractionators from these facilities is These criteria should not necessarily
characteristics notoriously poor. This can result in a govern the selection of the operation
Sulphur, nitrogen and aromatics content temporary spike in the content of the pressure. However, just barely exceeding
are the most important feed most difficult-to-treat sulphur these limits and requiring the next higher
characteristics that impact the process compounds in the hydrotreater feed and rated ANSI flange class in the reactor loop
design for diesel hydrotreating facilities. requires an increase in reactor will be very costly. Actual pipe wall
The nitrogen content of the feed has a temperature. This will increase the thickness is calculated for the design
significant impact on the required catalyst deactivation rate and, hence, conditions and the limiting value used
operating pressure for a new design. directionally reduce the cycle length. for the piping specification in the reactor

92 PTQ Q1 2009 www.eptq.com

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PTQ Q1 2009.indd 1 05/12/2008 10:00:41

loop alloy sections. The piping material hydrogen partial pressure. During the There are several ways to provide
selection between 321 and 347 stainless cycle, the increase in WABT will be 30– internal quench to the reactor to limit
steel can be optimised, based on design 50°F, with lower deactivation rates the temperature rise. The common
and operating temperature. Type 347 has occurring at higher hydrogen partial method is to utilise hydrogen-rich
a higher allowable stress value, as shown pressures. recycle gas/make-up hydrogen. The
in Table 1. quench gas also causes additional
For revamp designs, the hydrogen Reactor design vapourisation of some liquid in the
partial pressure achievable is restricted Initially, the reactor diameter is set to reactor, which provides an extra heat
by the existing equipment and piping obtain a superficial mass velocity (mass sink for reaction heat removal. Another
mechanical design and hydraulics in the flux) in the range of 2000–5000 lb/hr/ft2. less common approach is to recycle
reactor loop. A higher treat gas rate can A value of 3500 lb/hr/ft2 allows for a CHPS liquid to the reactor. As noted
be used to increase the hydrogen partial reasonable turn-down rate and some up previously, quench is added to limit the
pressure, but this is usually limited side allowance. The mass flow includes reactor bed temperature rise to 40–50°F.
because of the associated increase in the all hydrocarbon and hydrogen at the The reactor metallurgy is typically
reactor loop pressure drop and the reactor inlet. If the required diameter is 11/4 Chrome-1/2 Moly with 1/8in 347
corresponding maximum operating larger than the limit for which the stainless overlay or cladding. The choice
pressure of the various system reactor can be shop fabricated and often depends on the thickness of the
components. shipped to the plant site (12–14ft for vessel, which will affect the cost.
Make-up hydrogen purity impacts the over-land shipment), a two-train design Cladding is usually more economical for
hydrogen partial pressure for a fixed may be considered. For diesel vessels with wall thickness up to around
reactor operating pressure. Lower purity hydrotreaters, this is normally in the 4.0in. For greater thickness, overlay is
make-up hydrogen requires higher range of 30 000–40 000 bpsd per reactor normally used. For thick-wall reactors
hydrogen circulation rates to maintain train. For plants that have adequate with a minimum design metal
the target hydrogen partial pressure and water access and dock facilities, larger temperature of less than 0°F, 2 Chrome-
may even require a purge stream from reactors and thus larger single-train 1 Moly metallurgy may be the better
the cold separator. If the make-up capacities can be considered. choice.
hydrogen purity is too low, there is no For diesel hydrotreating, the flow
combination of recycle rate and purge through the reactor is two phase, so an Feed exchangers
that can be used to achieve the target appropriate correlation, such as that by The feed exchangers are generally
reactor outlet partial pressure. For a Larkins,4 is used for estimating the specified to optimise heat economy.
revamp design, increased make-up pressure drop. Inter-bed quench should However, enough duty should be
hydrogen purity is the most effective also be considered for the pressure drop allowed for the charge heater to have a
means of increasing the hydrogen calculation. The catalyst physical reasonable amount of turndown and
partial pressure. properties have a significant impact on overall heat balance control. The feed
For new designs, the cycle lengths the reactor pressure drop. This includes exchange should not be more than
have typically been set at 24–36 months. void fraction and equivalent particle about 80–85% of the total duty needed
This has been based on the logic that, at diameter. In order to ensure good to heat the feed to reactor temperature
some point, the cycle will be limited by distribution, most ULSD catalyst beds at end-of-cycle conditions.
factors other than catalyst activity: are dense loaded instead of sock loaded. For very low sulphur diesel product,
namely, reactor pressure drop. Hydrogen The calculated clean pressure drop the reactor feed/effluent exchangers’
partial pressure has a major impact on should be in the range of 0.5–1.0 psi per mechanical design requires special
cycle length from a catalyst activity foot of catalyst bed (clean). attention to minimise leaks. Many
standpoint. For a fixed space velocity, According to the required catalyst refiners prefer a pull-through tube
the cycle length increases with hydrogen volume, the bed heights are established bundle with a floating head because this
partial pressure. based on either the heat of reaction/ design is easier to clean and handle.
Maximum reactor outlet temperature maximum temperature rise or a bed However, the floating head cover is a
at end-of-cycle catalyst conditions is height of 30–40ft. The clean pressure potential source for leaks. A U-tube
generally set at 725–750°F to avoid drop is then estimated for each bed. The bundle avoids this potential problem
aromatics saturation equilibrium maximum overall pressure drop is and is less expensive. Also, tubes should
constraints. This is also influenced by determined for the design of the bed be seal welded to the tube sheet to
the quantity of cracked stocks in the support and to compare with the crush prevent leaks from the rolled tube
feed and the crude source. Hydrotreating strength of the catalyst. This value is the joints.
catalyst performance correlations for sum of the following: Materials selection for the feed/
reactor temperature are usually based on — Fouled bed pressure drop at 175% of effluent exchangers is based on predicted
the weighted average bed temperature calculated clean drop corrosion rates for the service conditions.
(WABT). WABT is calculated as the — Dead weight of catalyst and support The feed/effluent exchangers have
reactor inlet temperature plus two-thirds material several shells in each train in series with
of the reactor temperature rise. The — Coke deposits at 30% of catalyst varying metallurgy. The cold shells are
temperature rise is usually limited to dead weight all carbon steel. The intermediate
40–50°F per bed by quenching. Thus, for — Liquid hold-up temperature units normally have 11/4
a 50°F temperature rise and a 725°F — 15 psi allowance for depressurisation. chrome shells and 400 series tubes. The
maximum reactor outlet temperature, The pressure drop for the feed hot shells are 11/4 chrome with 300
the end-of-run WABT would be: distributor/redistributors, quench series stainless cladding and 300 series
internals and collector are added to the stainless tubes.
WABT = (725-50) + 2/3(50) = 708°F bed values to arrive at the overall fouled
reactor pressure drop. The design of the Charge heater
The start-of-run WABT has to be feed distributor and redistributors is As previously noted, the feed heater
sufficient to obtain the required removal crucial for obtaining the target product design duty should not be any less than
of sulphur and nitrogen. Cycle length is sulphur level. The distributors and approximately 20% of the combined
determined by the catalyst deactivation quench internals are usually catalyst feed duty to the reactor inlet temperature
rate at the design space velocity and vendors’ proprietary designs. at end-of-cycle conditions to allow for

94 PTQ Q1 2009 www.eptq.com

 At Saudi Aramco we
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barrels of oil every day.
Which is why we need
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www.ptqenquiry.com
for further information or text PTQREFINE2 to 63363
turndown and heat balance control. A with heaters with a required turndown to hydraulically limited in the reactor loop.
design margin of 10% of the combined less than 50% of design. This can be the This revamp would require, however, a
feed exchanger duty should be added to case with a charge heater with a low SOR modest increase in inlet flow and power
accommodate accelerated exchanger duty and a high design duty. In this case, for the recycle compressor.
fouling and loss of reactor heat of reaction the turndown can be 10–20% of design. Other options include the addition of
caused by removing highly reactive feeds Maximising energy efficiency can lead to hot and cold low-pressure separators.
such as FCC LCO and coker light gas oil. low SOR duty. High design duties are a These designs marginally unload the
The design duty of the charge heater result of off-design cases such as loss of upper part of the stripper and result in
should be checked to ensure it is sufficient reactive feed or cold start-up. improved LPG recovery. Figure 1
to bring the unit up to operating illustrates an ULSD hydrotreater with
temperatures from a cold start in a Reactor products separation HHPS/CHPS, Figure 2 an ULSD
reasonable length of time. There are several alternative hydrotreater with CHPS only and Figure
Typically, the number of heater passes arrangements for handling the reactor 3 a hydrotreater with HHPS/CHPS/CLPS.
matches the number of parallel feed/ effluent after the combined feed The HHPS base material is 11/4 Cr-1/2
effluent exchanger trains. The feed and exchangers. In general, the decision is Moly normally with clad or overlay. The
recycle hydrogen can be flow controlled whether or not to use an HHPS in lining is 300 or 400 series stainless,
for each train ahead of the exchangers, addition to a CHPS, or a CHPS only. The depending on the actual predicted
which will prevent any maldistribution HHPS is usually operated around 500– corrosion rate. For equipment in wet
of the two-phase stream entering the 550°F and, thus, the vapours can be used sour service, hydrogen induced cracking
heater passes. When there are more to heat recycle gas and cold separator (HIC) resistant carbon steel material
heater passes than feed effluent liquid. The HHPS improves the overall should be specified. This requirement
exchanger trains, particular care must be heat economy and results in a somewhat applies to the CHPS. A 300 series stainless
made to ensure equal distribution of smaller product stripper and auxiliary steel mesh pad is installed in the CHPS
vapour and liquid to each heater pass. equipment. This arrangement will also to assist in coalescing the wash water.
The limit for one heater pass is in the directionally improve the oil-water The boot of the CHPS should have 1/4in
range of 15 000–18 000 bpsd of fresh separation in the CHPS. For heavy gas corrosion allowance.
feed at typical diesel hydrotreater oil hydrotreating, a hot separator is
conditions. This limit is based on 8in practically mandatory to have adequate Reactor effluent air cooler
diameter maximum heater tubes and an oil/water separation. This is less of a Regardless of the reactor products
overall pressure drop of 40–50 psi. concern for diesel hydrotreating, unless separators configuration, a final cooling
Heater tube metallurgy is typically 347 there are significant quantities of cracked step is eventually used prior to separating
stainless steel. material, which decrease API gravity. liquid and vapour. An air cooler is
Environmental issues such as NOx and Disadvantages of this design are a 5–10% typically used, sometimes supplemented
CO emissions are also a concern in the lower recycle gas purity, which requires with a water trim cooler. Metallurgy
charge heater design. NOx emissions higher recycle hydrogen compressor selection of the piping and equipment
limitations are usually addressed by horsepower. The addition of a HHPS can in this area requires special attention
installing low NOx or ultra-low NOx be a viable option for debottlenecking because of the presence of ammonia and
burners. CO emissions can be a concern an existing hydrotreater that is hydrogen sulphide in the reactor

M. U. H2

Recycle M. U. H2
compressor compression

LCO Reactor
Feed
heater
SR diesel

Quench

Feed Amine
treating

ULSD product

Gas to fuel

CHPS
Sour water

Sour naphtha

Steam Wash water

Sour water

Figure 2 ULSD hydrotreater with CHPS only

96 PTQ Q1 2009 www.eptq.com

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 M. U. H2

Recycle M. U. H2
compressor compression

LCO Reactor
Feed
heater
SR diesel

Quench

Amine
Feed treating

ULSD product
Gas
Gas to
fuel CLPS

CHPS
Sour water
HHPS

Sour naphtha

Steam

Wash water
Sour water

Figure 3 ULSD hydrotreater with HPPS/CHPS/CLPS

effluent. As this stream is cooled, these Minimum velocity should be 10 ft/sec is not acceptable in most control valve
two compounds combine to form — Symmetrical piping in and out of sizing programmes. To bypass this
ammonium bisulphide (NH4HS), which the condenser problem, one of these two pressure
condenses as a solid on the inlet piping — Wash water source can be stripped values will need to be artificially
and in the cooler tubes. To prevent sour water, but should be from a stripper manipulated. If the vapour pressure is
plugging and under-deposit corrosion, dedicated to hydrotreating spent wash artificially reduced to below the critical
recirculating wash water is injected water service pressure, the effective pressure
ahead of the cooler, which introduces a — Wash water can be injected into the differential may be over-estimated and
corrosive aqueous solution in the main effluent line upstream of the air the control valve may be undersized.
stream. cooler or independently into each air Based on actual experience, the control
Tube metallurgy selection is based on cooler nozzle through a distribution valve vendors recommend that the
the product of the mole percentage of device such as a spray nozzle or restriction critical pressure is raised to equal to the
ammonia and hydrogen sulphide in the orifice. Injecting in the piping gives vapour pressure when specifying
total stream before water injection. The more time for mixing and vapourising instrument process data.
target maximum value for this product, the water and is less expensive. Injection
also know as Kp, is 0.15 (5) before alloy into individual air condenser nozzles Compression
metallurgy is considered: ensures good distribution in each of the The choice of recycle compressor design
air cooler bays. is based on inlet flow and head
KP = Mol % H2 S X Mol% NH3 < 0.15 If alloy construction is required, requirements. To use a centrifugal
typical alloys used are Incoloy 800 or compressor, adequate suction flow is
Other criteria include: 825 and duplex stainless steel 2205. required, but the head should be low
— Determine make-up water quantity enough to limit the number of stages,
to limit NH4HS concentration in the High-pressure separator liquid such that a single body machine can be
condensed water phase to 4 wt%. level control valve sizing used (usually maximum of ten stages). In
Assume equal molar amounts of In the high-pressure separator, the the past, most diesel hydrotreaters did
ammonia and hydrogen sulphide in the operating pressure is greater than the not have an adequate volume of recycle
CHPS water and that essentially all of critical pressure of the liquid. The high- gas for a centrifugal compressor. New,
the ammonia is dissolved in the water pressure separator liquid level control larger ULSD hydrotreaters circulating
— Determine circulating water quantity valve is in flashing liquid service. 3000–5000 SCF of gas per barrel of feed
as that needed to maintain a minimum Typically, both the vapour pressure and will be candidates for a centrifugal
of 20–25% of the total water injected in critical pressure are required to determine compressor. If a reciprocating compressor
the liquid phase ahead of the the effective pressure differential in the is used for recycle, it will normally be
condenser sizing of any control valve in flashing combined with the make-up service in a
— Mixed-phase velocities in the piping liquid service. In this case, the ratio of multiple-throw machine. For
and tubes should be limited to 20 ft/sec vapour pressure vs critical pressure is reciprocating compressors over about
for carbon steel and 30 ft/sec for alloy. greater than one. This unusual situation 500 HP, two 60% capacity machines are

98 PTQ Q1 2009 www.eptq.com

 make-up compression. This approach has
Typical pressure drop allowance for reactor loop equipment and piping in a the advantage of maintaining some
hydrotreater with reactor inlet pressure of 1100 psig hydrogen flow capability through the
Equipment item Pressure drop, psi reactor loop following a recycle
Combined feed exchangers (both sides) 40 compressor emergency outage.
Feed heater 50
Reactor (fouled) 75 Reactor loop hydraulics
HHPS vapour/recycle hydrogen (both sides) 20 A hydraulic profile is established for the
HHPS vapour/CHPS liquid 10 reactor loop in order to set the recycle
Reactor effluent air cooler 10 compressor head requirements and to
Amine/knock-out drums 5 establish the design pressure of the
Piping 23 piping and equipment.
Total reactor loop pressure drop 233 The reactor inlet pressure is set based
on conditions established by the catalyst
Table 2 supplier and, as noted previously,
considering the pressure limits of
Maximum pressure and typical design temperature for critical standard piping flanges. Table 2 shows
piping services in the reactor section the typical pressure drop allowance for
the reactor loop equipment and piping
Pipe section Design pressure, psi Design T, °F Max allowable, psi in a hydrotreater with a reactor inlet
Exchange to heater 1252 700 1260 pressure of 1100 psig.
Heater to reactor 1200 775 1242
A point-to-point pressure profile is
Reactor to exchange 1123 825 1233
shown in Figure 4. Data shown are for
the normal case (EOR) and for the
Table 3 relieving case when the CHPS is at 10%
above operating pressure. Table 3 is a
typically provided. For smaller lower molecular weight directionally tabulation of the maximum pressure (at
compressors, two 100% units are used. requires more head and potentially more relieving conditions) and typical design
The make-up compressor discharge stages. This is not as serious an issue with temperature for critical piping services
may be routed to either the recycle a reciprocating machine. However, higher in the reactor section. This is compared
compressor suction or discharge. Make- hydrogen purity will increase the to the maximum allowable pressure for
up gas flowing to the suction will increase discharge temperature, which is limited 900 psi, type 321 stainless flanges.
the purity and volume of the recycle gas per API-618 to 275°F. This analysis shows that the assumed
and decrease the molecular weight. Normally, the make-up would be pressure profile is consistent with the
Potentially, this could be a problem for a routed to the recycle compressor discharge use of 900 psi flanges in the reactor loop
centrifugal recycle compressor, since the unless this causes an additional stage of alloy piping. The relieving pressure

1054 M. U. H2
957
1198 1100 1200
LCO 1252
1102 M. U. H2
SR diesel 1152 compression
ΔP = 233
Reactor
Feed 1290
heater
1190
Quench Amine
Recycle treating
1274 1120 compressor
1025 1023
1174 1022 1060

Feed 963

1002
ULSD product
1100
1154

Gas to fuel 1254

1096
1186 1073 1065
1086
975 968
986 988

978
Sour water 1276
CHPS
1176 965 1062
1000
Sour naphtha
HHPS

Steam

Wash water
Normal Relieving Sour water

Figure 4 Normal/relieving pressure profile

www.eptq.com PTQ Q1 2009 99

 place, the fired reboiler option should be
Estimated equipment/materials delivery matrix considered. This will also create less sour
water to process.
Equipment materials Current quoted Vendor data submittal
The product stripper material of
deliveries (current durations)
construction is killed carbon steel with
Compressors (reciprocating) 70–92 weeks ARO 20 plus weeks ARO
(centrifugal) 70–84 weeks ARO 20 plus weeks ARO
410 SS trays and caps. Some part of the
Compressors (air) 52–64 weeks ARO 12–16 weeks ARO stripper column may need to be lined if
Centrifugal pumps (API) 36–52 weeks ARO 16 plus weeks ARO the H2S concentration is high. The
ANSI pumps 22–30 weeks ARO 10–12 weeks ARO overhead condenser and receiver are in
Agitators/mixers 26–28 weeks ARO 6-8 weeks ARO wet sour service and HIC-resistant steel
Reactors (ULSD/alloy) 18–24 months ARO 6–8 weeks ARO (outline) is required. The overhead receiver boot
Reactors (2 1/4 Cr. - 24–36 months ARO 6–8 weeks ARO (outline) has a 1/4in corrosion allowance. R/F
vanadium enhanced) >0.10 is typical for both steam stripper
Large towers (all metallurgies) 54–68 weeks ARO 6–8 weeks ARO (outline) and reboiled stripper.
Pressure vessels (carbon steel) 26–36 weeks ARO 4–6 weeks ARO (outline)
Pressure vessels (alloys) 48–56 weeks ARO 4–6 weeks ARO (outline) Feed filtration
Fired heaters 52–60 weeks ARO 12–14 weeks ARO Even though distillate stocks are relatively
(heater tubes - high alloy) 36–48 weeks ARO (mill delivery) clean, feed filtration is important to
Shell & tube heat exchangers 40–52 weeks ARO 6–8 weeks ARO reduce exchanger/reactor plugging. A
(carbon steel) cartridge filter with 25 micron retention
Shell & tube heat exchangers 52–80 weeks ARO 6–8 weeks ARO is typical for this application. Cracked
(alloys) feeds, if routed directly from the upstream
(ARO: After receipt of order) facilities, should not be cooled.

Table 4 Equipment delivery

Due to high worldwide demand, getting
profile will be used to set the design equipment and piping design information the necessary equipment delivered to
pressure of the equipment in the reactor is available, the settling-out pressure is the site could be a major challenge for
loop. Also, early in the process design, re-estimated to determine what margin is any project. Construction and
following completion of the heat and available compared to the CHPS relief installation schedules are often governed
weight balance and a preliminary process valve set point. If the settling-out pressure by the delivery of long-lead items. Table
flow diagram (PFD), a sized equipment exceeds the set pressure, a step-wise 4 gives an estimate of current equipment
list will be developed, which will allow calculation or dynamic simulation can be and materials delivery.
plot plan studies to be completed. used to estimate the relief rate.
Preliminary piping sketches of the References
1 Leliveld B, Mayo S, Miyauchi Y, Plantenga F,
reactor loop will be developed and the Product stripper Elegant solutions for ultra low sulphur diesel,
allowance for piping pressure drop In the product stripper, hydrogen 2001 NPRA Annual Meeting (AM-01-09).
rechecked prior to purchase of the sulphide formed in the reactor is 2 Brevoord E, Gudde N, Hoekstre G, Mayo
S, Plantenga F, ULSD real life: commercial
recycle compressor. The reactor loop removed from the diesel product along performance of stars and nebula technology,
hydraulics will be checked a final time with light hydrocarbons. The removal of 2002 NPRA Annual Meeting (AM-02-38).
following receipt of equipment vendor light material has to be sufficient to 3 Landue M V, Catalysis Today, 36, 1997, 393–
information and completion of piping meet a flash point specification of 130°F. 429.
4 Larkins R P, White R R, Jeffery D W, Two
isometrics for the reactor loop. This also ensures removal of essentially phase concurrent flow in packed beds,
Note that the design pressures in the all of the H2S. Approximately 30 trays AICHE Journal, June 1961, 231–239.
reactor loop were established by assuming are required in the column. Overhead 5 Piehl R L, Refiners tame effluent air-cooler
corrosion, Oil & Gas Journal, 18 August
the CHPS relief valve set pressure is 10% products include a sour gas, unstabilised 1975, 119–120.
above normal operating pressure. In fact, naphtha and sour water. Equipment is 6 Knudsen K G, Cooper B H, Topsoe H,
this margin can be 5% by using a pilot- included to provide intermittent water Catalyst and process technologies for ultra
low sulphur diesel, Applied Catalysis A:
operated relief valve, which will lower wash of the condenser. General 189, 1999, 205–215.
the design pressure of the reactor loop Steam or vapours from a fired reboiler 7 Torrisi Jr, S, Proven best practices for ULSD
equipment. Designing for a 10% margin are used as the stripping medium. Due production, 2002 NPRA Annual Meeting
(AM-02-35).
for a grass-roots facility allows room for to temperature constraints (about 700°F 8 Schmidt M, Premium performance
future capacity increases while staying maximum), the operating pressure of a hydrotreating with Axens HR 400 Series
within equipment design pressure limits. reboiled stripper is limited to around hydrotreating catalysts, 2002 NPRA Annual
Meeting (AM-02-57).
API recommended practice RP 521 40–50 psig. Unless the refinery has a 9 Palmer R E, Harwell L, Thakker S, Polcar
appendix G recommends the design low-pressure gas recovery system, a small S, Desai P, Design considerations for ULSD
pressure to be 105% of the settling-out compressor and spare will be required to hydrotreaters, 2003 NPRA Annual Meeting
pressure, which would make the design handle the off-gas. A steam stripper can (AM-03-89).
pressure about 115% of the normal be operated at over 100 psig, which
operating pressure. In the beginning of allows routing into an existing refinery R E (Ed) Palmer is Manager, Process
the process design stage when equipment sour fuel gas system. Design, Mustang Process Plants, Mustang
design conditions are being established, Diesel product from a steam stripper Engineering, Houston, Texas.
there is not sufficient information has to be further treated for water Email: ed.palmer@mustangeng.com
available to accurately calculate the removal. This can be vacuum drying or Stan Polcar is Process Engineering
settling-out pressure. However, when the coalescing, followed by salt drying. If Manager, Mustang Process Plants,
heat and material balance and PFD are this system is already in place, the steam Mustang Engineering, Houston, Texas.
completed, preliminary equipment sizing stripping option would definitely have a Email: stan.polcar@mustangeng.com
information and assumptions about pipe lower capital cost compared to a fired Anne Wong is Senior Consulting Technical
quantities along with the reactor loop reboiler. A steam stripped tower will also Professional, Mustang Process Plants,
pressure profile can be used to estimate be a little smaller than a reboiled tower. Mustang Engineering, Houston, Texas.
the settling-out pressure. When actual If the product drying system is not in Email: anne.wong@mustangeng.com

100 PTQ Q1 2009 www.eptq.com

www.ptqenquiry.com
for further information
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for further information
 Pygas upgrading for
European steam crackers
Upgrading secondary by-products from naphtha-based steam crackers is imperative to
remain profitable in a competitive petrochemical field. This article presents available
technology options for BTX recovery, styrene extraction, C5 olefin upgrading and more

Joseph C Gentryn and Meijuan Zeng

GTC Technology

I
n order to maintain competitiveness Downstream processing of cracked exceeds 400 KTA, butadiene, benzene
in the ethylene business for European hydrocarbons from liquid feedstocks and toluene production become
steam crackers, more emphasis must (naphtha and gas oil) is somewhat more economically feasible. At 600 KTA and
be placed on upgrading all of the by- complex than the processing of gaseous above, styrene extraction, production of
products that are generated by liquid feedstocks because heavier components C9 resins, xylenes, benzene derivatives
crackers. Producers who do not upgrade are present. In this case, a primary and C4 derivatives become economic.
these by-products will face increasing fractionator is installed upstream of the Isoprene, dicyclopentadiene (DCPD)
pressure on plant margins due to compressor to remove fuel oil, which is and piperylene recovery will be
competition from the low-cost regions produced in considerable amounts when economical at 800 KTA ethylene feed.
of the world. cracking naphtha or gas oil. This fuel is The steam cracker C5s have a variety of
Ethylene is one of the world’s most partly used in the direct quench end uses. These are often overlooked or
important chemical feedstocks. Together operation, while the remainder may be considered as orphan streams due to a
with propylene, it accounts for 50–60% sold or used as fuel for steam generation. lack of knowledge about end markets
of all organic petrochemical production. The primary fractionator also produces a and processing methods.
Most ethylene is produced via the steam gasoline stream, called pyrolysis gasoline Polyisoprene is a substitute for natural
cracking of hydrocarbon feedstocks such or pygas, which is rich in aromatics rubber, which is being constrained by
as ethane, propane, butane, naphtha or (benzene, toluene and C8 aromatics). land use in Southeast Asia that has been
gas oil. Steam cracking of saturated This pygas portion of the cracker set aside for palm oil plantations. The
hydrocarbons has been the dominant products contains a host of valuable supply/demand balance for isoprene has
technology for several decades. It petrochemicals that can be recovered if tightened in recent years, sometimes
involves thermal pyrolysis in the they are available in sufficientquantity resulting in sharp upward shifts in
presence of steam to dehydrogenate the and a suitable recovery method is pricing. Piperylenes (cis and trans 1,3
saturated hydrocarbon. Ethane crackers chosen. pentadiene) are used as a reactive
primarily produce ethylene and only Figure 1 provides a guideline of which monomer in the manufacture of plastics,
small amounts of co-products, whereas products may be economically recovered adhesives and resins. DCPD is used for
liquid crackers produce a range of olefins as a function of ethylene rate. With printing inks and as a precursor to
and aromatics, including butadiene, today’s typical increased cracker size, unsaturated polyester resins.
propylene and benzene. many of these products are economical After ethylene and propylene, benzene
West European ethylene production to produce. When the ethylene rate is the next most widely produced steam
is approximately 24 MM tpa, which
represents a 21% market share of
worldwide production. Naphtha and
condensates together provide 74% of
the feed to the European crackers; 13% Naphthalene,
of the feedstock is from NGL (ethane, secondary
%CONOMICAL PRODUCTS TO PRODUCE

derivatives
propane and butane), with the balance
being gas oil. On average, from 2008–
Isoprene, DCPD, pips
2011, ethylene capacity is expected to
increase by 3%.
In a relative sense, European steam Styrene extraction, C9 resins, xylenes,
benzene derivatives, C1 derivatives
crackers use more liquids in the feed
slate (eg, naphtha or gas oil) than Middle
Eastern producers, which use cost- Butadiene, benzene, toluene
advantaged NGLs. NGL-fed plants or gas
crackers are less complicated because Ethylene, propylene, primary derivatives
they require only a water quench
system and fewer process units for the
     
by-products. The main attraction for gas
%THYLENE RATE +4!
crackers is the lower feedstock cost, LIQUIDS FEED
which is often subsidised by national
governments and is lowest in the
Middle East. Figure 1 Economical products as a function of ethylene rate (liquids feed)

www.eptq.com PTQ Q1 2009 103

 Liquid-liquid extraction Extractive distillation
( / 2AFFINATE

2AFFINATE
%XTRACT

%XTRACT
&EED

&EED

3OLVENT

3OLVENT

Figure 2 Liquid-liquid extraction and extractive distillation

process wide-cut feeds instead of

Properties of Techtiv-100 extractive distillation solvent benzene-only in the ED configuration.
Previous generations of solvents could
Physical properties High-boiling; polar; non-nitrogen-containing components be used only with fractionated narrow-
Toxicity Low
cut feeds or with very high aromatic
Corrosivity Mild against carbon steel
content to avoid the situation of three-
Stability Thermally stable at design/operating conditions
phase distillation. The primary properties
Reactivity Non-reactive to feed components
Effective range 15% to >99% aromatics in the feed
of the solvent Techtiv-100 blend are
shown in Table 1.
The flow scheme of the GT-BTX
Table 1 process is quite simple (Figure 3). It
consists of two towers: an extractive
cracker petrochemical. Benzene has or sell the BTX cut to other units that distillation column (EDC) and a solvent
been denigrated as a cancer-causing recover the aromatics. Two technologies recovery column (SRC). The EDC cleanly
dangerous product. Government are used for BTX recovery: separates the aromatics and solvent into
legislators have deemed that the benzene — Liquid-liquid extraction (LLE) the bottoms from the solvent-free non-
content in motor gasoline should — Extractive distillation (ED). aromatics in the overhead. The second
generally be lower than 1 wt% worldwide The schematics of these two processes column strips the aromatics from the
and 0.62% in the US to protect the are shown in Figure 2. In the last few solvent, which is recycled back to the
citizens in these areas. While this has years, nearly all new units have been first column.
dampened the spirit for aromatics designed using ED technology, which Since the proprietary GT-BTX system
recovery, benzene, toluene and xylene offers a simpler design and better requires only two major unit operations,
(BTX) production is very much alive and process performance. it is easier to design and operate than the
needed, and somewhat encouraged by GTC offers the proprietary GT-BTX LLE processes. In LLE systems, the solvent
the need to remove the components process for aromatic recovery by ED. The makes an incomplete separation of the
from gasoline. In order to maintain working principle of ED is the alteration components at both ends of the extraction
competitiveness in the ethylene business, of the relative volatility of components column, thus requiring the additional
more emphasis must be placed on in the presence of a highly selective steps of extractive stripping and water
upgrading all of the by-products that are solvent. In a mixture containing washing of the raffinate. In GTC’s ED
available in the value chain of liquid aromatics and non-aromatics, the system, the ED column cleanly removes
crackers. relative volatility of the non-aromatic the non-aromatics from the aromatics,
components is enhanced over that of and the aromatics and solvent from the
BTX recovery the aromatic components in the presence raffinate, in a single operation. Therefore,
Figure 1 is not exact for every producer, of a solvent. This enhancement allows ED designs require fewer pieces of
but is a useful guideline to highlight the non-aromatics to be distilled equipment and a much lower capital cost
what typical commodity products could overhead in a conventional distillation than a LLE system or other ED systems
be recovered. Individual plant sites will column, while the aromatics are that require washing of products or
have different economies based on local recovered in the column bottoms. The reprocessing of the raffinate.
supply/demand, logistics of product solvent used in the GT-BTX process is Several variants of this technology
movements and construction costs. The the proprietary blend, Techtiv-100, can be used to revamp older LLE units
first priority for component recovery which makes it possible to achieve the based on sulpholane, NMP, NFM or
from the pygas is BTX. Most plants process performance with BT- or BTX- glycol solvent systems. GT-BTX PluS
already have aromatics extraction units containing feedstocks. Techtiv-100 can technology is used to separate aromatics

104 PTQ Q1 2009 www.eptq.com

 BASF

Process Technology – Americas

www.ptqenquiry.com Process Technology – Eastern Hemisphere
Arcadia. Contact: Mahin Rameshni for further information London. Contact: Steve Pollitt
Tel:+1 626 803 9058
Tel: +44 208 326 5258
Email: Mahin.Rameshni@worleyparson.com
Email: steve.pollitt@worleyparsons.com
London. Contact: Robin Street
Tel: +44 208 326 5421
Email: robin.street@worleyparsons.com
 %$#
CONDENSER 32#
#7 4O VACUUM
CONDENSER SYSTEM
,EAN SOLVENT
COOLER

7ATER 2AFFINATE

&EED 7ATER %XTRACT

Extractive
distillation
&EED column (EDC) Solvent recovery
PREHEATER 32#
%$# REBOILER column (SRC)
REBOILER -0 STEAM

-0
STEAM

3TEAM Solvent
Rich solvent regenerator
Lean solvent

7ATER 0URGE

Figure 3 Process flow scheme for GT-BTX process

plus sulphur from feedstocks that

contain olefins.
Heartcut distillation followed by ED
Styrene recovery
The next profitable component to ,IGHT
recover is styrene, extracted from the C8 # CUT
fraction of raw pygas. In a typical pygas #
#
operation, the styrene is hydrogenated 3TYRENE
to ethylbenzene (EB) in the pygas 0YGAS #  CUT  WT
hydrotreater units to reduce the gum-
# GT-Styrene
forming potential of the gasoline.
#
Unfortunately, this downgrades the # 
component value, consumes valuable (EAVY
hydrogen, uses capacity in the pygas CUT
hydrotreating unit and decreases the
potential value of the remaining xylenes.
Styrene cannot be purified by Figure 4 Conceptual arrangement for proprietary GT-Styrene process
conventional distillation because of the
presence of many other components scenarios. polymerisation, at a significant upgrade
with close boiling points. The process also provides other over its alternate value as a gasoline-
New technology that recovers the advantages by upgrading the xylenes blending component.
styrene from pygas via the ED method is (with lower EB content), reducing The analysis indicates that the
now being commercialised. The hydrotreater operating costs and extraction technology provides
proprietary GT-Styrene technology is hydrogen consumption, and increasing profitable production of styrene at
the most cost-effective process for hydrotreating capacity. Styrene is relatively small capacities. Prime
recovering styrene from untreated pygas. produced at high purity, suitable for candidates for the technology are
The economics are good for reasonable- ethylene producers that can generate
sized crackers using liquid feedstock. sufficient pygas feedstock to produce at
Prospective economics at current
The styrene extraction technology is least 20 000 t/yr of styrene. This would
pricing
applied to upgrade the styrene to include major naphtha-based steam
petrochemical value and to improve the Parameters GT-Styrene crackers in Europe, Asia and the
quality of the mixed xylenes. Figure 4 Capital cost, $ 30 MM Americas. The required capacity for GT-
shows the conceptual arrangement, Feedstock cost, $/tonne 850 Styrene is at least 15 000 t/yr contained
while Table 2 gives prospective Processing cost, $/tonne 250 styrene in pygas.
economics at recent pricing. A Total production cost, $/tonne 1100
proprietary solvent system, Techtiv-200, Sales price, $/tonne 1600 Olefin conversion to aromatics
is used to change the relative volatility Net margin 12.5 MM Other low-value steam cracker products
of the pygas components and allow the Pre-tax ROI, % 42 can be converted to additional BTX
styrene to be selectively extracted. The components with a novel aromatisation
cash cost economics are favoured over Basis: 250 000 MT/yr styrene technology. This process converts olefins
conventional styrene production from in the C4-C8 range into a mixture of C6-
benzene plus ethylene in all pricing Table 2 C9 aromatics. Typical feedstocks are the

106 PTQ Q1 2009 www.eptq.com

 EB Dealkylation
Further down the C8 chain, pygas
Regeneration gas xylenes can be selectively dealkylated to
produce isomer-quality material.
Flue gas Typically, pygas C8 streams have high
EB content and are not desirable for
Fired use as paraxylene plant feed. The
heater
proprietary EB Dealkylation process was
developed for increasing PX production
capacity by converting EB into benzene
plus ethane. Benzene product is high
Gas product purity (99.8 wt%) without extraction.
The ethane can be combined with
cracker feed to produce additional
Product ethylene. The technology features a
separation proprietary catalyst with high activity,
low ring loss and superior long
cycle length.
Liquid product Figure 6 shows a typical configuration
of EB Dealkylation with the GT-BTX
and GT-Styrene technology. The
feedstock is pygas C8. In the hydrogen
Feed environment, EB is dealkylated to
benzene with per pass conversion up to
100%, which results in very low
Figure 5 Scheme for the aromatisation process EB content in the mixed xylene
product. The xylene loss and ring
mono-olefin C4 or C5 fractions, or the for feeding into a paraxylene complex. loss are very low even at high EB
olefinic C6-C8 fractions from partially Figure 5 highlights the aromatisation conversion. The low EB xylene product
hydrotreated pygas. C4s usually come process. can be either sold on the market at a
from the raffinate after BD extraction, The aromatisation takes place in a premium price or used in a paraxylene
the raffinate after i-butene extraction for single-stage adiabatic fixed-bed reactor, recovery plant to debottleneck
MTBE, or a mixture of the above. C5s which operates in a cyclic mode of production. Benzene and the small
include raffinate after isoprene and CPD regeneration. The operation is very amount of toluene generated can be
extraction, partially hydrotreated C5s, or simple, with no hydrogen required. The sent to the fractionation section to
a mixture of these. C6-C8s are the olefins reactor is operated at 460–540°C and the produce on-spec products. Highlights of
from partially hydrotreated pygas. pressure is 1–4 bar. Catalyst lifetime is the EB Dealkylation process are:
Another feed source is from refinery greater than two years. The liquid yield — Simple, low-cost fixed-bed reactor
FCC gasoline after removal of the of aromatics is approximately 47–55%, design
aromatics. In the aromatisation process, depending on feedstocks. By-products — Flexible feedstocks and operation
olefins and naphthenes convert at are dry gas and LPG, with yields of 15– — Stable catalyst with long operating
approximately a 1:1 ratio into aromatics. 20% and 30–35% respectively. Separation life
The products are rich in xylenes and of liquid aromatics products may be — Low hydrogen consumption
xylene precursors, and therefore useful accomplished by simple fractionation. — Moderate operating parameters.

#

"ENZENE TOLUENE
# #

2ECYCLE 8YLENES
2AFFINATE ## LOW %"
3TEAM 2AFFINATE '4n"48
.APHTHA CRACKING CONVERSION '4n"480LU3
#S
EB &'
# #S ## ##
( Dealkylation
ST STAGE
( HYDROGENATION
Distillation

Distillation

Distillation

#

'4 3TYRENE
#S

# #
3TYRENE

Figure 6 Combinations of GT-BTX, GT-Styrene and EB Dealkylation

www.eptq.com PTQ Q1 2009 107

 Heating
media

Cooling
media
Water
Melt
purifier
Lights
PGO feed Naphthalene
fractionator
Aromatic
solvent
Lights
removal Lights
column (recycle)

Treatment 80°C NAP

79°C NAP
Solvent
flasher
Finish
column
Heavy recycle

PGO bottoms

Figure 7 Naphthalene separation process

Naphthalene the static freezing technique, slurry with benzene by-product. Naphthalene
In the heavier cut of pyrolysis gas oil handling is avoided, which simplifies recovery from PGO is profitable when
(PGO), naphthalene can be recovered. the operation. The system is also reliable. the cracker size crosses the 1000 KTA
When a cracker size crosses the 1000 No moving devices such as filters or mark. Otherwise, PGO is traditionally
KTA mark, naphthalene recovery is centrifuges required, so the investment consumed as fuel for boilers or sold at
economically feasible. The method of and operating costs are reduced. heating value.
choice is a static-melt crystallisation In summary, there are a number of
process, such as that used at the largest Conclusions new processes that are applicable to the
North American producer’s site. This Although European crackers may be C5+ spectrum of by-products from
operation produces refined naphthalene disadvantaged on the basis of pure naphtha-based steam crackers. In order
with a MP of 80°C, along with aromatic ethylene production, these units can to maintain a competitive position, a
solvents and speciality fuel products. maintain a viable and profitable cracker operator needs to consider taking
Various product derivatives can further operation if the by-products are advantage of all the possible upgrade
increase the profitability of naphthalene strategically upgraded. Many of the opportunities presented.
recovery. The generic flow scheme of secondary products are economical to
heartcut fractionation followed by produce at ethylene rates as low as 600
crystallisation is shown in Figure 7. KTA. The key to realising this value is an This article is based on a presentation at the
recent ERTC Petrochemical Conference in
Naphthalene is available in three understanding of the range of products Cannes, October 2008. GT-BTX, Techtiv-100,
grades (MP based): 78°C, 79°C and 80°C. that are possible to produce and utilising Techtiv-200, GT-BTX PluS, GT-Styrene and EB
Refined naphthalene from PGO the latest process technology for the Dealkylation are marks of GTC Technology.
feedstock is clear, with low levels of petrochemical upgrades.
sulphur. Major sections of the process BTX recovery is basic for all crackers,
involve prefractionation and crystallis- and it is economical at a cracker capacity
ation operations. Prefractionation uses as low as 400 KTA. ED technology has Joseph C Gentry, PE, is Director of
distillation to produce a concentrate of replaced LLE due to its simplicity and Technology for GTC Technology, Houston,
naphthalene. The melt purifier employs increased performance in separating Texas. His responsibilities include
progressive freezing in a static device close boiling components. ED technology technology alliances and acquisitions,
with no moving parts and low equipment also makes styrene recovery from pygas technical sales and process technology
cost. Optional operations are used to viable for reasonable-sized crackers using licensing. Email: jgentry@gtchouston.com
produce 79°C and 80°C naphthalene liquid feedstock. Advanced aromatisation Meijuan Zeng, PhD, is a Process Engineer
from 78°C naphthalene. technology transforms low-value steam for GTC Technology, Houston, Texas,
The process design using static melt cracker C4-C8 products to higher-value working on petrochemical and biofuel
purification is the cheapest way to BTX components. EB Dealkylation is technology developments.
produce high purity naphthalene. With useful to produce high-quality xylenes Email: mjzeng@gtchouston.com

108 PTQ Q1 2009 www.eptq.com

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 Control of primary
fractionator fouling
Optimal operation and chemical treatment of primary fractionators requires an
in-depth knowledge of many parameters. A combination of analytical tools and
benchmarking information can help predict fouling severity

Bob Presenti, Dan Frye and Sandra Linares-Samaniego

Nalco Company

T
he ethylene industry remains agglomeration and deposition of Stream characterisation
extremely competitive. Fouling polynuclear aromatic hydrocarbons and benchmarking
in primary fractionators costs (PNAs). The primary fractionator is usually the
ethylene producers millions of dollars Top section fouling is usually first tower after the transfer line
annually in lost production, product identified by increased differential exchanger (TLE) or furnace. The primary
downgrades, reduced energy efficiency pressure (DP) and increased overhead functions of this unit are heat recovery
and unplanned shutdowns. The endpoint. While increased DP can limit and crude fractionation of the furnace
primary fractionator in a liquid cracker the throughput and decrease the unit effluent. Basic plant configurations vary
represents one of the largest potential run length, an elevated pygas endpoint widely from plant to plant, but most
material and energy cost debits if fouling can lead to emulsions in the quench fractionators have a top stream, bottom
is not controlled. While the fouling water loop and product downgrades stream and a light fuel oil stream. Due
mechanisms in primary fractionators downstream. to the variability in design and operating
have been studied extensively over the Fouling in the bottoms section of a conditions, a comprehensive approach
past few decades, they are by no means primary fractionator will cause changes to primary fractionator treatment and
fully understood. in the viscosity control of the circulating monitoring that includes the
The overlying problem for most quench oil, loss of heat recovery, a characterisation and benchmarking of
ethylene producers is the ability to decrease in dilution steam production, the process streams was undertaken.
effectively monitor the impact of an increase in pump energy usage and Figure 1 shows the sampling points and
fouling on primary fractionator poor filter operation, as well as many summarises some of the tests undertaken
performance. Often, proper other issues. on each of these streams.
instrumentation is either unreliable or
non-existent and plant operators are
challenged to answer the questions “Is
my tower fouling?” and, if so, “What
do I do to stop it?”. As part of Nalco’s Reflux
QWT
Best Practices primary fractionator • Soluble polymer
treatment programme (PrimAct), • Reactive monomers
• Iron
benchmarking, analytical and • Specific gravity
monitoring tools have been developed • Other
to give ethylene producers an improved
tool to evaluate fouling tendencies.
This in turn helps us understand and
optimise the economic impact of
fouling and operational optimisations. Light side draw
• Existent gums
• Polymer content
Fouling in a primary From TLE • Naphthalenes
fractionator • Other
Primary fractionator fouling can be
broken down into two distinct problem
areas: top section fouling and
bottom section fouling. The fouling Quench oil Heavy side draw
mechanisms in the top and bottom • Polymer content • Existent gums
sections of a primary fractionator are • Pentane insoluble • Polymer content
quite different. Analyses of top sections • Viscosity • Pentane insoluble
of fractionators across the industry
• Other

indicate that the predominant fouling

mechanism is the deposition of cross-
linked polystyrene-type polymers
formed through free radical
polymerisation, whereas fouling in the
bottom section of the primary
fractionator is caused by the Figure 1 PF survey sampling points and testing

www.eptq.com PTQ Q1 2009 111

 benchmarking data for reflux streams is
included on the following pages in
25 Figures 2 to 5.
Reviewing the benchmarking data in
Styrene Figures 2 to 5 reveals that stream
Indene
20 DCPD
characterisation is plant specific and
that further investigation is required
before the fouling severity in a tower
15 can be predicted based on analytical
Percent

data. Still, several observations exist

based on Nalco’s initial survey of reflux
10
streams:
— Styrene content alone does not
5 predict fouling severity, as polystyrene
is very soluble in styrene
— Styrene and indene levels are
0 independent of each other (Figure 2).
Plant #1 Plant #2 Plant #3 Plant #4 Plant #5 Plant #6 Plant #7 Plant #8
Indene will cross-link with polystyrene
to form a polymer that is less soluble in
the liquid stream
Figure 2 Average reactive monomer in reflux — DCPD is present when the reflux
contains recycle streams (Plants 1, 2, 3
and 7 in Figure 2). DCPD reacts via a
Diels-Alder mechanism to both form
0.8 polymer and cross-link with other
oligomers and polymers like
0.7 polystyrene
— Iron does not appear to exist in
0.6
significant quantities (Figure 3).
0.5 Specific gravity of the reflux stream
(Figure 4) is indirectly controlled as
ppm

0.4 each ethylene operator attempts to

maximise pygas flow while maintaining
0.3 stream endpoint within a targeted
0.2
range. As specific gravity approaches
1.0, the potential for emulsion and
0.1 separation problems in the quench
tower and downstream equipment
0.0 increases.
Plant #1 Plant #2 Plant #3 Plant #4 Plant #5 Plant #6 Plant #7
Figure 5 summarises the soluble
polymer levels in the reflux using a
Nalco proprietary lab method. This
Figure 3 Average iron levels in reflux data is interesting not only because it
demonstrates significant variation in
soluble polymer from plant-to-plant,
but also because the levels in some of
0.96 the reflux streams are much higher
0.95 than previously anticipated. This
0.94
suggests that in addition to the
polymerisation occurring inside the
0.93
tower, polymer is being formed at
0.92 varying levels outside of the primary
Specific gravity

0.91 fractionator and transported back to

0.90
the tower via recycle streams or the
quench tower gasoline reflux.
0.89
0.88 Field monitoring techniques
0.87 development
0.86 Many ethylene producers have become
0.85
frustrated with conventional monitoring
Plant #1 Plant #2 Plant #3 Plant #4 Plant #5 Plant #6 Plant #7 Plant #8 techniques like delta pressure (DP) as a
measure of fouling in the upper section
of a primary fractionator. Two goals to
Figure 4 Average specific gravity of reflux address this problem have been
identified. The first involves the
A database of analytical results from and serves as a benchmarking tool for application of statistical modelling to
ethylene plants throughout the world other units. Currently, the database is improve the ability to detect fouling in
is being compiled and continues to comprised of towers that have DP trends. The second is to develop
grow, as over 400 samples have been experienced fouling problems as we other monitoring techniques to support
analysed to date. This database allows work with each ethylene producer to the DP analysis. Figure 6 outlines
for continuous expansion of knowledge improve reliability. A portion of the Nalco’s initial statistical modelling of

112 PTQ Q1 2009 www.eptq.com

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the operating envelope of equipment and process resulting in production
decrease, loss of revenue and profit

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 900

800
700
600

500

ppm
400

300

200
100
0
Plant #1 Plant #2 Plant #3 Plant #4 Plant #5 Plant #6 Plant #7 Plant #8

Figure 5 Average soluble polymer in reflux

!CTUAL
!CTUAL n -ODELLED $0
MEASURED FOULING
]
]
PrimAct
started

Figure 6 Actual modelled DP using statistical modelling

one plant’s primary fractionator with respect to a baseline, thus providing

tower DP. a tool for monitoring operational or
Using statistical modelling software, chemical treatment changes in the
three separate models were created and unit, as can be observed from Figures 7
compared. The models helped smooth and 8.
the DP trend and remove hydraulic
impacts. This analysis offers an Primary fractionator
improvement over traditional flow- monitoring
corrected multivariate regressions of Figures 7 and 8 illustrate that the field
tower pressure drop by addressing methods were useful tools to evaluate
limitations due to non-linearity and operational modifications, as well as
autocorrelation of “independent” changes in chemical treatment. In the
variables typical of actual plant previous example, the data was used to
operations.
In addition to focusing on statistical
modelling, two proprietary field “The optimal operation
analytical methods were developed to
measure the polymer content in the and chemical treatment
reflux and the light side stream. The of primary fractionators
results from the new field methods
have correlated strongly with other is a very complex issue
proven soluble polymer methods, such
as that outlined in Figure 5, but the
that requires an in-depth
advantage to the field methods is that knowledge of many
results can be obtained within minutes
on-site. These methods allow for robust
parameters”
comparison of relative polymer content

114 PTQ Q1 2009 www.eptq.com

understand questionable tower DP data,
a problem that haunts many ethylene
producers. By trending the ratio of the

amount of polymer exiting the upper
section in the light fuel oil to the &OULING RATIO  ,IGHT SIDE STREAM POLYMER LB
 2EFLUX POLYMER LB
amount of polymer entering the tower
in the reflux (fouling ratio), we were 
able to measure analytically the impact
of chemistry and operational changes.  Untreated
A higher fouling ratio translates to
more polymer being produced in the 
upper section of the tower. In the end,

&OULING RATIO
the reduction in fouling ratio supported 
the statistical modelling trends, showing
that PrimAct had reduced fouling and 
flattened a previously upward DP trend.
The field methods were also used to test 
the efficacy of the inhibitor used in the
PrimAct program. Figure 8 outlines the  Start
PrimAct
results of a plant test, where samples
were taken before and after increasing 
the inhibitor dosage. In this fouled
tower, the plant theorised that polymer 
was entraining overhead. This theory 4IME
was substantiated, as both the reflux
and light fuel oil levels decreased when
the inhibitor dosage increased.
Figure 7 Fouling ratio improves with Nalco PrimAct
Current landscape
Currently, Nalco’s industry database
includes 15–20 primary fractionators as
of the end of 2008 and is expected to
continue expanding. The knowledge  
gained thus far has allowed for the  2EFLUX 
development of the previously  ,IGHT FUEL OIL

2EFLUX POLYMER INDEX

discussed monitoring tools and their Avg. reflux MPI = 112

,&/ POLYMER INDEX


Avg. LFO MPI = 1050 
implementation at four plants, yielding 
a better understanding of fouling and 
 Avg. reflux MPI = 53
its impact on plant total cost of Avg. LFO MPI = 813


operation (TCO). At one plant where 

fouling was an issue and potentially 
threatened ethylene production targets, 
 
the combination of the field polymer
method, economic tools and the 


        
chemical treatment programme allowed $AYS
the plant to survive until the scheduled
turnaround. At other plants, anywhere
from $3–10 MM of annual TCO savings
have been identified to justify chemical Figure 8 Polymer levels decreased when Nalco PrimAct inhibitor was increased on the
treatment, so that operational fifth day
optimisations can proceed. Examples of
TCO items include the following: fractionator treatment programme This article is based on a presentation from
— Reduction of polymer formation in requires a flexible and wide-ranging the October 2008 ERTC Petrochemical
Conference in Cannes, France. PrimAct is a
the top section to allow more pygas approach that includes the development registered trademark of Nalco.
production of analytical and monitoring tools,
— Controlling the bottom temperature benchmarking data and modelling
at a higher level without fouling or loss tools. While only a small portion of
of viscosity control. the current work has been described
As the industry database expands, it and discussed, it nonetheless reveals
will provide an enhanced capability to an example of the challenging nature
help ethylene producers compete in the of the problems faced, as well as Bob Presenti is Key Account Manager with
highly competitive ethylene market. the possibilities that further Nalco Company in Sugar Land, Texas.
understanding of the system can afford. Email: bpresenti@nalco.com
Conclusion The first goal has been to innovate with Dan Frye is Global Industry Development
The optimal operation and chemical new monitoring techniques that Manager, Ethylene, with Nalco Company
treatment of primary fractionators is a translate to economic optimisations. in Sugar Land, Texas.
very complex issue that requires an in- Looking forward, Nalco believes the Email: dkfrye@nalco.com
depth knowledge of many parameters, combination of these analytical tools Sandra Linares-Samaniego is Senior
as well as a deep understanding of with benchmarking information will Researcher with Nalco Company in Sugar
parameter interplay. For this reason, a help towards predicting fouling Land, Texas.
comprehensive Best Practices primary severity. Email: slsamaniego@nalco.com

www.eptq.com PTQ Q1 2009 115

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There are several ways of meeting emission limits, but SOx and NOx reduction
additives are very attractive as they require little or no capital investment and have
reasonable operating costs, resulting in an overall lower cost than a WGS or SCR

Chris Kuehler, Pieter van de Gender and Subramani Ramachandran

Albemarle Corporation

I
ncreasingly severe regulation of States.2 Integrated pollution prevention Coke formed in the FCCU cracking
sulphur oxide (SOx) and nitrogen and control is based on a permit system process is subsequently burned to both
oxide (NOx) emissions from FCCUs for installations. The Directive does not regenerate the catalyst and supply the
is being implemented around the set standards or thresholds for the heat required for vapourisation and
world. Although there are a variety prevention and control of emissions, or cracking. Depending on the character of
of approaches for meeting emission for other environmental aspects, but the feed, 5–10% of the feed sulphur
limits, the use of SOx and NOx reduction leaves this responsibility to the Member reports to the coke and is quantitatively
additives appears to be very attractive States. The IPPC Directive applies to oxidised to SO2 and SO3 (SOx). Left
technically and economically. both new and existing installations (ie, uncontrolled, SOx concentrations in the
SOx and NOx emissions from many those built before 2000), where the regenerator flue gas can reach into
industrial sources have long been operators intend to carry out changes the thousands of ppm, depending on
regulated worldwide. In the US, in that may have significant negative feed quality.
addition to possible state and local effects on human health and the
regulations, SOx and NOx emissions from environment. Member States were given FCCU SOx reduction
FCCUs have been most recently a transitional period until October 2007 technology
impacted by an Environmental to ensure all other existing installations The means for reducing SOx emissions
Protection Agency (EPA) programme of fully comply with the Directive. from the FCCU regenerator fall into
civil enforcement of the Clean Air Act In contrast to the US, where the three categories:
(CAA). Citing alleged violations of the consent decrees set limits on individual — Lowering the sulphur in the feed
CAA, the EPA has entered into FCCUs, most countries in Europe look at — Treating the flue gas downstream
settlements (consent decrees), which emissions from a “bubble” point-of- from the FCCU
provide for both possible fines and view. Local authorities issue permits — Use of a SOx reduction additive
mandatory implementation of pollution based on Best Available Technique (BAT). within the FCCU.
control technology. BATs, documented in Best Available Lowering the feed sulphur can be
Since March 2000, the EPA’s national Technology Reference documents achieved through the purchase of lower
Petroleum Refining Priority Program has (BREFs), have been developed for sulphur feeds and by hydrotreating.
resulted in 21 settlements with US individual industrial processes by the Both of these approaches can be
refiners, accounting for approximately exchange of information among experts expensive, although they bring other
86% of the nation’s refining capacity.1 from industry, Member State authorities, benefits, such as improved yield structure
These settlements, covering 95 refineries, research institutes and non-governmental and lower sulphur levels in liquid
will result in an estimated $5 billion organisations (NGOs). The original products, and they must be judged on
investment in control technology with BREFs are currently being updated. the overall economics. If the refiner is
an annual reduction in SOx emissions of In the rest of the world, a variety of faced with a low SOx emission limit, it
245 000 tonnes. The consent decrees local, regional and national systems may also be difficult to meet with these
cover a variety of emission sources, but regulate gaseous emissions from FCCUs. approaches alone.
there is a heavy focus on the FCCU. In South America, each country has There have been a variety of processes
The consent decrees generally different regulations. For example, in developed for the removal of SOx from
prescribe the implementation of Brazil, SOx from the FCCU is limited to flue gas, but the dominant technology
emission reduction technology, but in 1200 mg/Nm3, while in the industrial has been the wet gas scrubber (WGS)
some cases refiners accept hard limits for regions near Buenos Aires, Argentina, using caustic as a reagent to regenerate
the FCCU flue gas, which they meet by there is a 500 mg/Nm3 regulation. the scrubbing liquid. This technology
methods of their choice. The ultimate has been commonly mandated under
SOx emission target for all refiners is SOx emissions the consent decrees and is included
25 ppmv. The corresponding target for SOx emissions from industrial sources under BATs in the EU. In a later portion
NOx emissions is 20 ppmv. have been a problem since the Industrial of this article, the economics of this
In the 27 countries of the European Revolution, with the most visible technology relative to SOx reduction
Community, the emissions situation is manifestation being acid rain caused additives are discussed.
addressed by the Integrated Pollution from burning coal. In recent years, more
Prevention and Control (IPPC) Directive focus has been put on other industrial Background to SOx
adopted in 1996 by the EU and sources such as petroleum refineries, reduction additives
subsequently transposed into the where a major source of SOx is typically An SOx reduction additive (or SOx
national legislation of EU Member the FCCU.3 transfer additive) is designed to pick up

www.eptq.com PTQ Q1 2009 117

 SOx in the FCCU regenerator and release
it as H2S in the reactor. This is illustrated
Regenerator: schematically in Figure 1. In the late
SO2 + 1/2 O2 SO3 1970s, Akzo Nobel Catalysts (now
MeO + SO3 MeSO4
Albemarle) developed and patented the
Reactor products: use of hydrotalcite (HTC) as a SOx
¾ 35% of feed sulphur H2S
¾ 55% of feed sulphur Products reduction additive4 and has continued
Flue gas:
¾ 10% of feed sulphur to develop this technology.5 This is a
Coke S Regenerator: layered magnesia-alumina system with
SOx MeS + H2O MeO + H2S the advantage of being rich in
magnesium, which results in improved
Riser reactor: SOx pickup compared to competitive
MeSO4 + 8 ‘H’ MeS + 4 H2O
MeSO4 + 8 ‘H’ MeO + H2S + 3 H2O technology.
Since this development, Akzo Nobel
licensed the HTC technology to the
Feed, containing industry. In 2002, the company began
sulphur
marketing its own additives (KDSOx/
Air SOxDown) with improvements in SOx
pickup efficiency and physical properties
that ensured retention of the additive in
the unit. In subsequent years, HTC
Figure 1 Sulphur in fluid catalytic cracking technology has accounted for
approximately 70% of the SOx reduction
technology used in the refining industry.
SOxDown is a subsequent improvement
of the KDSOx additive.

A common measure used to gauge the
+$3/X effectiveness of a SOx reduction additive
#OMPETITOR is the pickup factor (PUF). This is defined
3/X PICKUP FACTOR KG 3/XKG ADDITIVE

as the weight of SOx removed per weight


of additive used. The weight of SOx
removed is calculated by estimating the
mass rate of SOx that would have been
emitted using correlations for

uncontrolled SOx and then subtracting
the mass rate of SOx leaving the
regenerator while using the additive. The
PUF can vary with operating conditions,

in particular additive loading.

Case study 1
VGO operation with a high

        sulphur feed
!DDITIVE USAGE KGDAY Data comparing KDSOx and a competitive
additive are shown in Figure 2 for a 50
000 bpd UOP high efficiency
Figure 2 Comparison of KDSOx to competitive additive configuration operating in full
combustion. Feed sulphur is fairly high
at 2.0 wt%. The PUF for KDSOx is
approximately 40% higher than of the

competitive product.

3/ X $OWN Case study 2

3/X PICKUP FACTOR KG 3/XKG ADDITIVE

#OMPETITOR Resid operation

The next example comes from a modified
 Kellogg Model III unit feeding some
resid. Regenerator temperature is typically
higher than 732°C. A high regenerator
temperature can significantly reduce the
effectiveness of a SOx reduction additive.
 In addition to increasing the hydro-
thermal deactivation rate, the equilibrium
of SO3 to SO2 is less favourable. Figure 3
illustrates that at severe regenerator
conditions, SOxDown shows a 20%
 advantage over a competitive product.
     Even so, an ongoing R&D programme
!DDITIVE USAGE KGDAY
has been devoted to new products aimed
at improving SOx reduction in situations
where SOx additives have been previously
Figure 3 Comparison of SOxDown to competitive additive challenged.

118 PTQ Q1 2009 www.eptq.com

 COnveRt
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www.ptqenquiry.com
for further information
 deactivation of SOxMaster and
conventional additives in commercial
units. Data from four commercial trials
100 are shown: two trials with conventional
additives and two with SOxMaster. These
commercial data demonstrate the
80 superior stability of SOxMaster.
Conventional additives lose half of their
Relat ive SOx reduct ion

60
initial activity within days. With
SOxMaster, lower SOx emissions continue
for several weeks or months after additive
40 addition is stopped.
Conventional additive – trial 1
Conventional additive – trial 2 Case study 3
20 SOxMaster - trial 1 FCCU in deep partial burn
SOxMaster - trial 2 In case 3, an FCCU processes heavy VGO
0 with an average sulphur content of 1.8
0 5 10 15 20 25 30 35 40 wt%. The regenerator runs in deep
Days after addition is stopped partial-burn mode; the average CO
content of the flue gas during the trial
was 7.3 mol%. Average riser and
Figure 4 Commercial examples of SOxMaster performance regenerator temperatures were 527°C
and 691°C respectively. The inventory
refreshment rate in this unit is high:
daily additions are about 4% of the unit
15 100 inventory.
Figure 5 illustrates the SOx reduction
that was achieved. This refinery managed
12 80 an impressive 90% reduction in SOx
emissions compared to the typically
Additive in inventory, wt%

SOx reduction, % maximum achievable of 40%. This

9 60 example clearly demonstrates that SOx
reduction improves as the level of
SOxMaster in the unit inventory is
6 40 building up. With conventional
additives, SOx emissions are strongly
dependent on daily additive dosage.
With SOxMaster, due to the longer half
3 20
life, additive built up in the inventory
SOxMaster in inventory
SOx reduction also contributes to the overall SOx
reduction achieved.
0 0
0 20 40 60 80 100 120 140 160 180 200
Days Case study 4
FCCU in full burn with very low
daily replacement
Figure 5 Commercial examples of SOx reduction using SOxMaster In case 4, an FCCU changes frequently
between high sulphur (HS) and low
Enhanced SOx reduction — Superior stability under commercial sulphur (LS) VGO. The regenerator is
The intrinsic activity of SOx reduction FCC conditions operated in full combustion. Several
additives has improved considerably — Improved regenerability SOx additives from different suppliers
over the past few decades. Many refiners — A lower sensitivity to the availability have been tried in this FCCU without
have no doubt benefited from these of O2 in the regenerator (better success due to the low inventory
conventional SOx additives. In parallel performance in partial-burn units). replacement rate. Daily additions are
to these additive developments, there is SOxMaster is suited for R2R FCC only about 0.5 wt% of the unit
an awareness that many FCCUs are applications, which run with partial inventory. SOxMaster was recom-
failing to meet SOx reduction targets, burn in R1 (first regenerator) and high mended to achieve the target 50% SOx
such as when: temperatures in R2 (second regenerator). reduction with HS feeds.
— Operating in deep partial-burn mode Additional benefits with this more During the trial, the average sulphur
— Operating at high regenerator sophisticated formulation, compared to content was 1.6 wt% for HS and 0.5
temperatures conventional additives, are its wt% for LS feeds. Average riser and
— Operating with low daily replacement contribution to E-cat activity and unit regenerator temperatures were 508°C
rates conversion. Hence, FCC catalyst and 673°C respectively.
— The refinery/FCCU is subject to very consumption can be reduced. It also has Figure 6 shows the results of the
low SOx emissions. a lower CO promotion activity. SOxMaster trial. As predicted, SOx
For these more difficult applications, The use of conventional additives in emissions during HS campaigns could
additional capabilities that are not deep partial-burn regenerators can upset be halved with 10–12 wt% additive. Of
available from conventional SOx additives the CO2/CO balance, leading to higher course, SOx reductions are even better
are required, which is why Albemarle CRC and regenerator temperatures. The with LS feeds, thanks to lower
developed the SOxMaster additive. It use of SOxMaster will have a much uncontrolled SOx emissions. On average,
includes features that are not available smaller effect on regenerator operation the SOx reduction during LS campaigns
from conventional additives, including: in deep partial burn. Figure 4 shows the was 80%.

120 PTQ Q1 2009 www.eptq.com

 This commercial trial again shows
that the percentage SOx removal is not
determined by daily additive additions, HS feed
but correlates with the amount of 100 14
SOxMaster in inventory.
80 12
Selection of the best
SOx additive 60 10

SOx reduction, %
Until recently, all available SOx additives

Additive, wt%
40 8
had high initial intrinsic activity but
limited stability under commercial FCC
20 6
conditions. These types of additives are
still the best choice for the easier
0 4
applications, where relatively small
quantities of additives are enough to SOx reduction
–20 2
achieve the target SOx reduction. SOxMaster, wt%
SOxDown is recommended here, as it –40 0
has the highest initial intrinsic activity. 0 20 40 60 80 100
Situations that favour the use of high Days
activity SOx additives are:
— Regenerators that operate in full
burn or at low CO levels
— Low to moderate regenerator
LS feed
temperatures
100 100
— Moderate to high daily replacement
rates 80 80
— Moderate SOx reduction targets.

Relative SOx reduction

There are also many cases where the 60 60
high initial pickup of SOx by fresh
SOx reduction, %

additives is not sufficient to meet SOx 40 40

reduction targets. Large amounts of fresh
additive would be required in these cases, 20 40
resulting in severe activity dilution of the
FCC catalyst inventory. For these units, 0 20
almost all the SOxMaster additive that is
–20 SOx reduction 20
present in the FCCU inventory contributes SOxMaster, wt%
to SOx reduction. In contrast to
–40 0
conventional additives, the SOx removal 0 20 40 60 80 100
is not determined by fresh additive Days
additions, but by the total amount of
additive in inventory. Situations that
favour the use of SOxMaster are: Figure 6 Results of SOxMaster trial
— Regenerators that operate in deep
partial burn — Hydrotreat FCC feed: big investment planning and are highly effective. They
— High regenerator temperatures but normally high return value are in widespread usage under the
— Low daily replacement rates — Flue gas scrubbing (WGS) with consent decrees in the US and are
— Low SOx emission targets. caustic: moderate investment, net costs included as a BAT in the EU.
Albemarle has developed a proprietary — FCC SOx reduction additive: The process aspects of a WGS also
SOx model that explains the commercial minimal/no investment, sulphur is need to be considered. There can be
performance of additives in all FCCUs. recovered pressure drop issues, especially if located
This model accounts for the activity of — Low sulphur FCC feed selection: no downstream from a CO boiler. Use of
fresh SOx additives, the effect of operating investment, higher crude cost. caustic (NaOH) vs magnesium hydroxide
conditions, and the deactivation and The first option often makes economic (MgOH) is an economic vs operational
regeneration of these additives in sense when adequate capital is available. issue. MgOH costs less but has poorer
commercial operations. The economics of the last option vary solubility, resulting in more erosion/
With this model, it can be determined day-to-day with the spread between fouling of pumps, control valves,
if an FCCU requires a conventional SOx high and low sulphur crudes. The middle exchangers and pipes. Sulphate
additive, or if the high stability of two options will be reviewed in this deposition in the wash water piping
SOxMaster is the best choice. section, with a focus on the process and system can lead to plugging of pipes and
economic issues associated with their valves, and there is a need to avoid
SOx reduction additives commercial applications. exceeding a certain level of
vs scrubbers In comparing the installation of a concentration of solids (0.5 wt% is a
As discussed earlier, SOx emissions are scrubber to using a SOx reduction typical maximum value). Even then,
being increasingly regulated around the additive, a number of points need to be there are issues with the erosion of
world. Fortunately, refiners have options considered. Using additives to remove pump impellers in the circulation water
to meet the mandates. Expanding on SOx actually prevents pollution; pumps and the need for abrasion-
the list of options mentioned earlier, scrubbers convert the air pollution to resistant coatings. With everything in
primary commercial options include, in potential water pollution. A WGS good order, there can still be problems
descending order of capital investment consumes valuable resources such as with the formation of a visible plume
(not necessarily in order of total costs vs energy and water, while additives do from the WGS stack, with sulphites/
benefits): not. Additives require minimum sulphates deposition in the near vicinity.

www.eptq.com PTQ Q1 2009 121

 potential option for mitigating the regen
side corrosion was to reduce SOx in the
regenerator itself through the use of a
80
SOx reduction additive. The refiner
decided to use SOxDown, while the
SOx reduction, %

60 effective SOx reduction provided by the

additive allowed the refiner to turn
40 down caustic consumption.
Figures 7 and 8 illustrate the effect of
the additive on SOx levels and caustic
20
SOxDown started usage. With a target removal rate of
50%, actual reductions averaging 67%
0 were observed. At the same time, caustic
0 20 40 60 80 100 120 140
Days usage was cut by more than 60%.
In the case of this refinery, using the
additive permitted a 15% reduction in
Figure 7 Effect of SOxDown on SOx levels operating costs in the scrubber, with the
sole yield shift a small increase in fuel
gas H2S, as expected. The additive use
was more than paid for by the reduced
200 2.5 scrubber costs. Lower SOx also reduced
the level of corrosion in the regenerator,
180 2.0 an ongoing concern. Given these
favourable results, the refiner continued
Feed, m3/hr

Caustic, m3/hr
160 1.5 to use SOxDown even with a scrubber in
SOxDown started place. This example clearly illustrates a
140 1.0 case where refiner is finding it
Caustic
economically viable to use reduction
120 0.5
Feed additives even with an installed WGS.
100 0.0
0 20 40 60 80 100 120 140 Economic comparison of WGS
Days and SOx reduction additives
There are contrasting cost trends for
WGS and SOx reduction additive
Figure 8 Effect of SOxDown on caustic usage technologies. Additive costs increase
more than linearly as the degree of
removal increases. As you would expect,
Cost comparison of scrubber and SOxDown scrubber total costs decrease as the
investment is amortised over larger
% reduction 25% 50% 90% amounts of removed sulphur, although
$/kg SO2 removed Total costs 3.7 2.2 1.6 the operating costs increase linearly.
(scrubber) Additive use reduces these. More
Operating costs 1.05 0.92 0.86 generally, you can estimate the
$/kg SO2 removed Daily costs 0.40 0.46 0.70 economics for ranges of sulphur removal,
(additive) comparing total scrubber costs to
additive use. An added economic benefit
Table 1 that you need to consider is the value of
product sulphur, which is generated
Other aspects to consider are: water, which can be substantial in from the extra H2S in the sulphur
— Operational flexibility during a some cases. Most of the remaining recovery plant. This economic value also
shutdown, especially the need to have variable costs track caustic use (power, needs to be considered in the comparison,
an emergency sump to store the water process water, water and solids disposal). but is location specific. For example,
— Sludge disposal costs The total variable costs are over 40% of China values this product, while some
— Loss of the potentially valuable the scrubber total cost (including places (eg, Canadian oil sands plants)
sulphur by-product. amortised fixed investment) at design have little to no market for sulphur. Not
removal rate. considering the value for by-product
SOx additive usage with a As an example, a recent application of sulphur, the economics have been
commercial scrubber SOxDown in a Middle East refinery with compiled for several levels of removal
It is clear that additive use could prevent an existing scrubber is reviewed. This efficiency: 25, 50 and 90%. Scrubber
(or at least postpone) the decision to FCCU processes 30 000 bpsd of 100% costs are taken from a Belco publication.6
install a scrubber. After the capital has atmospheric resid, with a high sulphur Capital costs were escalated at a nominal
been spent, however, it is still possible to content at 2.7 wt%, and 4 wt% 4%/y from 2000 to present, while
compare additive use to scrubber Conradson carbon, operating in full operating costs were only adjusted for
operation, neglecting the sunk burn. Severe corrosion was observed the increase in caustic, since this is the
investment costs. over a period of time, with sulphur large part of such costs. Caustic price has
Typically, the major component of a deposits found in the regenerator. The increased in this period from
scrubber’s variable (operating) costs, refiner experienced frequent problems approximately $160/tonne to $400/
caustic usage, is a direct function of the associated with corrosion, resulting in tonne.
amount of feed sulphur reporting to blocking of cyclone paths, catalyst losses Table 1 compares full costs of scrubber,
flue gas. However, location specifics and subsequent shutdowns. Detailed operating costs only and the daily costs
might influence the costs of power and investigation had indicated that one of SOxDown. The overall conclusion is

122 PTQ Q1 2009 www.eptq.com

 1° Pyrolysis

BORSIG
HCN 2° Oxidation

N (coke) H2O N2 , NO, NO2

O2
NH3
Leading Technology for
3° No reduction
Innovative Solutions
2 NO + 2 CO N2 + 2 CO2
C + 2 NO N2 + CO2 BORSIG ZM
Compression GmbH
z Reciprocating Compressors
Figure 9 NOx Formation in fluid catalytic cracking for process gases and CNG filling
stations
z Centrifugal Compressors
that additives are very competitive to install in WGS systems, z Blowers
even at very high removal requirements. Even after a WGS has
been installed, the specific costing situation can favour additive
use through reduced scrubber operating costs. Scrubber costs BORSIG Process Heat
are specific for each location (especially caustic and sulphur Exchanger GmbH
values), while additive costs are less variable.
z Process Gas Waste Heat
Recovery Systems
NOx formation in FCCU flue gas z Quench Coolers
Approximately half of the nitrogen in the feed to an FCCU z Scraped Surface Exchangers
reports to coke. When this coke is burned in the regenerator of a
unit operating in complete combustion, about 10% of the coke
nitrogen is released as NOx (primarily NO). A simplified illustration
BORSIG Membrane
of the chemistry is illustrated in Figure 9. Technology GmbH
It is generally agreed that there is little, if no, contribution to
z Membrane Systems for Gases
NOx from thermal oxidation of N2. NOx is formed by oxidation and Vapours
of nitrogen compounds such as hydrogen cyanide (HCN) and z Vapour Recovery Units
NH3 formed by pyrolysis reactions. It is consumed by reduction, z Product Recovery Units for
primarily by CO. Thus, the concentrations of oxygen and CO Ethylene, Propylene and other
Hydrocarbons
in a regenerator are very important in determining the ultimate
NOx level in the flue gas. In addition, any catalysts present that
will influence these reactions will affect NOx. BORSIG Boiler Systems
In a regenerator operating in full combustion, the objective GmbH
z Fired Boilers
is to burn the coke as fully and effectively as possible to CO2 to
z Heat Recovery Boilers
minimise CO emissions. The strategy for accomplishing this in
z Combined Heat and Power
a typical bubbling bed regenerator is to provide plenty of Systems
oxygen and catalyse the oxidation of CO using a Pt catalyst. In z Boiler and Power Plant
addition to being very active for CO oxidation, Pt is very Engineering
effective for oxidising nitrogen-containing intermediates in this
oxygen-rich environment. At the same time, CO concentration BORSIG Service GmbH
is very low and little reduction of NOx occurs. This environment
leads to high levels of NOx. z Industrial and Power Plant
If a regenerator is designed efficiently, it can operate with Services
little or no CO combustion promoter. An example of this is the for plants in the energy and power
combustor design, which produces a relatively low level of NOx. station sector, chemical and petro-
chemical industry, as well as oil, gas
In any event, Pt promoter usage and excess oxygen should be and water supply applications
minimised within constraints to reduce NOx emissions.
A contrasting mode of regenerator operation is partial For more information, please contact:
combustion. Insufficient oxygen is provided for complete
combustion of the coke and the flue gas can contain up to 10
vol% CO. Typically, no Pt promoter is used. All of these BORSIG GmbH
conditions favour the minimisation of NOx and, in fact, NOx Egellsstrasse 21
levels in the flue gas leaving the regenerator are typically very D-13507 Berlin / Germany
low. However, to meet CO emission limits and to recover the
fuel value of the CO, the flue gas is usually incinerated in some Phone: +49 (0) 30 / 4301-01
sort of boiler. These typically operate at 900–1000°C and Fax: +49 (0) 30 / 4301-2236
introduce the possibility for the generation of thermal NOx. In e-mail: info@borsig.de
addition, unoxidised nitrogen intermediates now have the www.borsig.de
opportunity to be converted to NOx.
There are a number of regenerator configurations that A member of the KNM Group Berhad
operate with two stages, one in full combustion and one in
partial, with various routings of the flue gas streams. The issues

www.ptqenquiry.com
for further information
www.eptq.com PTQ Q1 2009 123
 with NOx for these systems are covered
by the individual arguments previously
NOx emission and after burn
made.  
First truck with ElimiNO x
Reduction in NOx emissions  
There are essentially four approaches to
reducing NOx in the FCCU regenerator  

4EMPERATURE ²#
flue gas:

./X PPM
— Optimisation of operating conditions
 
— Mechanical design changes
— Downstream flue gas treating
 
— Catalytic additives. 40–45% NO x reduction
For a given regenerator configuration,
minimising excess oxygen and Pt  ./X PPM 
!FTER BURNING Last truck with ElimiNO x
promoter usage are the simplest options
for reducing NOx emissions in full  
       
combustion. Of course, these must be $AYS
done in the context of CO emission
limits and afterburn constraints. In Figure 10 Effectiveness of ElimiNOx in commercial application
partial combustion, operations can be
optimised in the CO boiler to minimise
NOx. Avoiding over-firing the boiler to
raise additional steam is an example 140
of this. Initial dose Second dose
0.09 wt% 0.18 wt%
Mechanical design changes generally 120
focus on spent catalyst distribution,
combustion/lift air distribution and
NOx stack emissions, lb/hr

100
regenerator mixing intensity. All of these
can be utilised in full burn to increase 80
regenerator efficiency, allowing
operation at the conditions that 60
minimise NOx previously described. A
good example of achieving lower NOx
40
through improved combustion efficiency Zero daily
is the two-stage combustor design, additions Additions Additions
20
which utilises a fast fluidised bed and Fresh catalyst Fresh catalyst
catalyst recirculation. This regenerator 0.1 wt% 0.25 wt%
0
can operate at low excess oxygen and –40 –20 0 20 40 60 80 100 120 140
generally without Pt promoter. Days
With proper distribution, the carbon
on spent catalyst can also be utilised as a
reductant via the second reaction in the Figure 11 Effectiveness of KDNOx in commercial application
figure above. A good example of this is
the counter-current regenerator design
in which the spent catalyst distributor is Comparison of the various NOx control approaches for a typical
designed to distribute the carbon-rich 28 000 bpd FCCU
catalyst evenly across the surface of the
bed, reducing the NOx in the flue gas Technology Efficiency, Installation cost, Operating cost, Specific removal cost,
leaving the bed. Baffles can be used in % $ million $ million/yr $/tonne NOx
the bed to promote this counter-current SCR 85 2.1–6.3 0.21–0.84 3600
SNCR 60–80 0.6–2.6 0.09–0.70 3000
operation.
ElimiNOx 40–70 0.32–1.76 1200–3600
In partial combustion, proper design
KDNOx 30–80 0.11–0.22 2400–3600
of the CO boiler can minimise NOx.
Examples of good design practice include
the use of low-NOx burners for Table 2
supplemental fuel gas and staged
combustion, with optimised balance of — Selective catalytic reduction (SCR) the flue gas, it can be converted to SO3
the air to each stage. — Selective non-catalytic reduction by the SCR catalyst and this will react
Of course, taking advantage of (SNCR) with the ammonia to form ammonium
mechanical improvements requires — LoTOx (scrubber required). sulphate and bisulphate, which can
hardware modifications and capital In SCR, NOx is reacted with ammonia cause plugging in downstream units and
expenditures. In many cases, a given and oxygen over a catalyst, most particulate emissions. Another drawback
regenerator configuration is simply not commonly vanadium pentoxide/ to SCR is the use of a structured catalyst
suitable for some of these design titanium dioxide. Operating temperature support, which is sensitive to particulates
changes. is relatively low (350–375°C) for this in the flue gas.
The third approach to NOx reduction catalyst system and efficiency can be In SNCR, NOx is reacted with ammonia
is treatment of the flue gas downstream quite high. Ammonia is added, but there or urea at much higher temperatures
of the regenerator and CO boiler. This is usually sufficient oxygen already in than SCR (900–1000°C). A CO boiler
generally requires capital investment the flue gas. The net products are water with adequate residence time is required,
and additional operating cost. The three and nitrogen; however, some ammonia so SNCR is generally only applicable in
processes developed to do this are: remains in the flue gas. If there is SO2 in partial combustion. NOx reductions are

124 PTQ Q1 2009 www.eptq.com

lower than those achieved by SCR and themselves, as discussed earlier. SNCR are not consumed by emission reduction
the process suffers from the same requires a CO boiler. Both have an additives. Even if a WGS exists, SOx
ammonia slip problem. operating expense in the reactant. reduction additives can be cost effective
LoTOx involves reacting ozone with Table 2 compares the economics of through reduction in caustic costs.
NOx. A scrubber is required and operating the various approaches for a typical
costs can be high. This process has had 28 000 bpsd FCCU. The investment and SOxMaster (SOxMASTER), SOxDown
(SOxDOWN), ElimiNOx (ELIMINOx), KDNOx and
limited application. operating costs for the hardware KDSOx are marks of Albemarle Corporation.
approaches come from the 2003 EU
Catalytic additives for BREF escalated to 2008.7 The ranges
NOx reduction represent potential variations in References
Albemarle offers two catalytic solutions technology performance, degree of NOx 1 EPA website: www.epa.gov/compliance/
resources/cases/civil/caa/oil/index.html
for reducing NOx in FCCU regenerator removal, and uncontrolled NOx level. 2 Questions and Answers on Implementation
flue gas in full-burn operation: ElimiNOx Operating cost for ElimiNOx is the of the Integrated Pollution Prevention
and KDNOx. incremental over using a Pt promoter. and Control Directive: http://europa.
eu/rapid/pressReleasesAction.do?
If an FCC is using a Pt-based CO The principle conclusion is that reference=MEMO/05/ 403&format=HTML
combustion promoter, replacing it with additive technology for NOx reduction is &aged=0&language=EN&guiLanguage=en
ElimiNOx is the first step towards economically competitive with hardware 3 Levelton Engineering and Pervin & Gertz,
reducing NOx emissions, effectively without the need for capital investment. Benchmarking of Refinery Emissions
Performance, prepared for Canadian
oxidising CO and controlling afterburn, Council of Ministers of the Environment,
but it is much less active for oxidising Conclusions July 2003, S-5.
nitrogen compounds. Typically, NOx Increasingly severe regulation of SOx 4 van Broekhoven E H, US Patent 4 866 019,
September 1989.
levels while using ElimiNOx are 40–70% and NOx emissions from FCCUs is being 5 Stamires, et al, US Patent 6 593 265,
lower than those observed from a Pt- implemented around the world. December 2003.
based promoter. Figure 10 illustrates Although there are a variety of 6 Gilman K, Eagleson S, Weaver E, Controlling
FCCU regenerator emissions, World Refining
the effectiveness of ElimiNOx. approaches for meeting emission limits, 2000.
ElimiNOx has been used successfully the use of SOx and NOx reduction
in more than 20 applications around the additives appears to be very attractive.
world and is approved for usage under These options require little or no capital Chris Kuehler was Technology Manager,
EPA consent decree agreements. It has investment and have reasonable FCC additives, Albemarle Corporation,
proven to be more active than operating costs, resulting in an overall Houston, Texas. He is currently employed
competitive products, lowering required lower cost than a WGS or SCR. In by Chevron Research, California.
usage as much as 50%. contrast to hardware approaches, Pieter van de Gender is Senior Technical
While ElimiNOx suppresses the additives prevent pollution and do not Consultant, FCC, Albemarle, Amersfoort,
formation of NOx, KDNOx reduces the transfer it to a potential liquid or solids The Netherlands.
level of NOx by catalysing its reduction disposal problem or increased particulate Subramani Ramachandran is Technical
by CO. Figure 11 illustrates the emissions. Energy and water resources Consultant, Albemarle, Singapore.
effectiveness of KDNOx in a commercial
application.
In this case, NOx was reduced by ★

approximately 50% by using 0.25 wt%

of KDNOx on catalyst additions. The
performance of a NOx reduction additive 3rd
is naturally sensitive to the concentration

refining
of CO, one of the reactants. Thus,
conditions like low excess oxygen favour
NOx reduction, while poor air distribution
renders the additive less effective.

China
★

★
Performance is also influenced by
regenerator design. Commercially, NOx
reductions as high as 80% have been ★
observed, but there have been instances

2009
where reductions were quite low. Using ★
ElimiNOx for combustion promotion
favours the performance of KDNOx. As ★
with ElimiNOx, KDNOx has been widely
used and is approved by the EPA for

17–18 March 2009

consent decree applications.

Additives vs hardware
Additives like ElimiNOx and KDNOx
offer flexibility and the virtue of little or Beijing
no capital expense. A loader may be
required. However, as discussed earlier,
they may not be effective in all The networking event of the year for everyone
applications and may not be able to with an interest in refining technology in China.
reach very low NOx limits.
SCR has the potential for consistently Combine it with a visit to CIPPE, 19-21 March
meeting low NOx limits, but requires
significant capital investment and
www.refiningchina.com
maintenance. The units are sensitive to
particulates and can produce particulates

www.eptq.com PTQ Q1 2009 125

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 SO2 scrubbing in
refinery applications
Emissions control and by-product capture can add value from flue gas streams generated by
FCCU, process heaters, sulphur plants and spent acid regeneration units. Process flow sheet
information and utility consumption guidelines are presented for an SO2 scrubbing system

Rick W Birnbaum
Cansolv Technologies

T
ighter regulations, an increasing
spread between sweet and sour
1.6 33.5
crude prices, and attractive
revenue opportunities for sulphur and its 1.4 33.0
by-products have led refiners to increase
Sulphur in crude
their use of high sulphur fuels internally 1.2 32.5
and install flue gas desulphurisation
Sulphur in crude, wt%

systems to capture SO2. 1.0 32.0

API gravity
The Cansolv SO2 scrubbing system API gravity
0.8 31.5
has been in use commercially since 2002
and a total of nine units are now 0.6 31.0
operating worldwide. These units capture
SO2 from FCCU regenerator offgas, fluid 0.4 30.5
coker CO boiler offgas, lead and copper
smelter offgas, sulphur plant tail gas and 0.2 30.0
sulphuric acid plant tail gas. 0 29.5
1/84 1/86 1/88 1/90 1/92 1/94 1/96 1/98 1/00 1/02 1/04 1/06 1/08
Higher API gravity and Date
sulphur content
Environmental pressures and refining
costs are two challenges that face refiners Figure 1 Trend of sulphur content and density of average US crude diet (Source: EIA)
on a daily basis. The spread between
sweet and sour crudes is increasing as for example, would drop by nearly $900 refiner to incorporate these materials
supplies of sweet crudes become tighter. MM annually if the refiner were able to into their refinery fuel balance.
Environmental pressures continue to take advantage of the full spread between Cogeneration or heater refuelling
tighten, reducing the refiner’s options to light and heavy crudes. projects can absorb part of an
dispose of high sulphur products into However, various technical issues unmarketable bottoms stream, but
the marketplace, into the air or into must be addressed in order to take additional SOx, NOx and particulate
refinery wastewater streams. advantage of the price gap between light controls will be needed to accommodate
Long-term trends for crude feed and heavy crudes. By definition, heavy the use of poorer quality fuels
quality to refiners are clear. For example, crudes produce a heavier slate of products — Increasing prices for natural gas or
the US EPA, through its Energy containing greater amounts of sulphur. refinery gas will incentivise the refiner
Information Administration (EIA), Major investments in bottoms processing to conserve these commodities for use as
reports that the average diet of crudes capacity are required that would also hydrogen plant feed. Converting process
fed to US refineries has become heavier need additional investments in hydrogen heaters from gas to oil may be
and higher in sulphur content over the and hydroprocessing capacity for all justifiable
last 25 years. Figure 1 shows the overall products, and additional sulphur — Demand for fertilisers by India,
trend. In 1984, the average refinery was conversion capacity. Processing schemes China and the worldwide biofuels
fed 32.7 °API oil containing 0.9 wt% must also be reviewed to ensure product markets is expected to continue to exert
sulphur. In 2008, these numbers changed quality does not suffer. Additional pressure on sulphur and its by-products
to 30.3 °API and 1.4 wt % sulphur. On a investment may be needed to preserve for the foreseeable future. If by-product
planning basis, it would not be octane, cetane and vapour pressure sulphur prices remain high, regenerable
inappropriate to anticipate that crude in requirements of distillate products or to SO2 capture projects will be better
20 years’ time might consist of 28.3 °API remove benzene and other aromatics positioned to serve refinery-wide
oil containing 1.8 wt% sulphur. generated by new bottoms processing emission reduction campaigns
Oil price trends are also clear. The cost units. Changing markets for bottoms — Higher alkylate demand, higher
of crude is rising and the split between products, tighter environmental sulphuric acid costs and tighter markets
the cost of heavy and light crudes has regulations and increasing costs for for acid may compel the refiner to install
grown to nearly $10/Bbl. The incentive natural gas will require renewed examin- standalone spent sulphuric acid
to configure the refinery to process these ation of utility systems, such that: regeneration (SAR) systems. Excess acid
cheaper, opportunity crudes is significant. — Shrinking markets for high sulphur capacity, beyond alkylation needs,
The cost base of a 250 000 bpd refinery, residuum or coke will incentivise the would provide an additional outlet for

www.eptq.com PTQ Q1 2009 127

 trend for the same refinery as it might
appear in the future. The crude mix is
 KBPD  3TD 3 heavier and contains more sulphur. The
LIGHT TO 77 product volumetric split is now 58%,
 KBPD DISTILLATE 25% and 17% between light, intermediate
 WT 3  3TD 3 and bottoms products respectively.
 KBPD  3TD 3 (YPOTHETICAL TO AIR
 ²!0) (YPOTHETICAL Figure 3 also shows how the overall
53 REFINERY MIDDLE 53 REFINERY
 DISTILLATE  sulphur balance might look, assuming
 3TD 3
TO PRODUCTS that sulphur emissions to air and water
have been curtailed, FCCU SO2 is
 KBPD  3TD 3 captured in a regenerable scrubber and
BOTTOMS TO 325 cogen facilities have been installed to
burn up to 15 kbpd of residuum or its
equivalent in coke. The total amount of
Figure 2 Crude and sulphur scenario for average US refinery in 2008 sulphur fed to the refinery increases to
697 short tonnes per day (St/d). 1.0%,
14% and 85% of the sulphur entering
with the crude leaves with waste streams,
 3TD 3
 KBPD
TO 77
product streams or via the SRU
LIGHT respectively. Four significant changes to
 KBPD DISTILLATE
 3TD 3 the refinery utility and sulphur systems
 WT 3
 ²!0) (YPOTHETICAL  KBPD  3TD 3 (YPOTHETICAL TO AIR are assumed to support the sulphur
53 REFINERY MIDDLE 53 REFINERY distribution scenario for the future
 DISTILLATE 
 3TD 3 refinery:
TO PRODUCTS — Half of the 30 000 bpd bottoms
 KBPD stream is retained as fuel due to soft
 3TD 3 markets for high sulphur fuel oils. The
BOTTOMS TO 325
balance is sold to remaining markets for
high sulphur fuels. SO2 is captured from
the combusted resid flue gas stream in
Figure 3 Crude and sulphur scenario for average US refinery in future the SO2 scrubbing system and directed
to the SRU
H2S generated by the refinery, a partial produced by a Claus SRU and a SAR — FCCU regen gas SO2 is captured and
backup to existing sulphur recovery unit directed to the SRU through the
units (SRUs) and a second revenue — An SO2 scrubbing system will soon installation of a SO2 scrubbing system
stream for sulphur. be operating in a coal-fired cogeneration — A SAR has been installed to regenerate
Environmental pressures must also be facility in China. This unit captures SO2 spent alkylation acid catalyst and to act
addressed. Permits to expand or modify from a 240 MW power facility and as a contingency disposal point for acid
processing units will void “grand- directs the SO2 by-product to a sulphuric gas in the refinery. SO2 is directed to the
fathered” emissions allowances and acid unit. The by-product revenue from acid plant from the SO2 scrubbing system
force the installation of additional end- this project will pay for the capital costs to secure a sulphur emission rate of less
of-pipe wastewater and flue gas treatment within three years than 0.3lb of sulphur per tonne of acid
systems. Tighter environmental emission — SO2 scrubbing systems have also made
limits can be met by redirecting sulphur been licensed to refiners who will use it — A SRU SO2 tail gas unit is assumed to
compounds that are now discharged to capture SO2 from flue gas generated be required, which increases the refinery
into the wastewater and the air to other by resid fired crude unit process heaters SRU conversion efficiency to over 99.9%.
disposal points, such as the SRU. and utility boiler systems. SO2 is routed back to the SRU.
Many of the strategic pressures facing In each case, an SO2 scrubbing system
the refiner will require additional Refinery SO2 scrubbing is required to manage the additional SO2
attention to be paid to its overall sulphur Figure 2 shows the overall processing that is emitted as a consequence of the
balance. Non-regenerable SO2 scrubbing trend for a hypothetical 250 000 bpd changes. By directing resid to fuel
systems will only increase costs as the refinery today. It assumes a 60%, 30%, systems, an additional 96 tonnes of
cost for reagents such as sodium 10% split between light distillate, heavy sulphur must be captured as SO2.
hydroxide, lime or limestone increase. distillate and bottoms product Redirecting SO2 from the FCCU scrubber
Further, tighter environmental controls distributions. For simplicity, volumetric away from the wastewater treatment
will likely limit the ability to dispose of shrinkages or gains between feed and systems increases the sulphur load on
gypsum to landfill or to dispose of product streams are not considered. the SRU by 27 tonnes per day (tpd). The
sodium sulphate into refinery wastewater Refinery gas production is ignored. A tail gas system adds an additional 12 tpd
streams. Regenerable SO2 scrubbing 250 000 bpd refinery is assumed to of SO2 load on the SRU.
systems can help ease many of the produce 250 000 bpd of products from Four cases have been developed to
environmental- and market-induced the same volume of crude. illustrate how a regenerable SO2
pressures that are associated with the Figure 2 also shows the overall sulphur scrubbing system can be used for each
use of greater quantities of opportunistic balance that might apply to such a case previously described. Inside battery
crudes. The Cansolv SO2 scrubbing refinery. A total of 535 short tonnes (St) limits (ISBL) costs have been estimated
system has been able to satisfy all of of sulphur are contained in the crude and operating costs have been derived
these SO2 capture needs previously feed. 5%, 25% and 70% of the sulphur to satisfy utility, operations and
described, including: entering the refinery with the crude is maintenance costs of the SO2 system.
— FCCU and fluid coker CO boiler flue assumed to flow to air and wastewater Revenue from sulphur by-products is
gas SO2 scrubbing applications for two streams, product streams and to the also estimated to illustrate how by-
years SRU respectively. product revenues can impact project
— Since 2002, for removal of SO2 Figure 3 shows the overall processing economics.

128 PTQ Q1 2009 www.eptq.com

 Prescrubber Amine purification Regenerator
unit (APU) O/H system
4O 325
Utility boiler Battery
limits 4O STACK
economiser
air to air exchange !05

ESP

&UEL Amine
absorber Regenerator
!IR

"OTTOM 3TEAM
ASH
&LY 7ASH (/
ASH

7ASTE (/
Combustion system Flue gas pretreatment SO2 management
"OILER 3/ REMOVAL n 3"37%30 3/ CAPTURE
!IR TO AIR EXCHANGE $UST REMOVAL n $RY %30 3/ REGENERATION
1UENCHCOOL n 0RESCRUB

Figure 4 Cogen system flue gas treating flow diagram

By-product values — The SO2 management system. MM for utilities, consumables, operation
Changing crude prices have rippled Cost and utility data have been and maintenance. The revenue
through the economy and created established for the flue gas prescrubber opportunity for sulphur generated from
similar, related waves in sulphur by- and the SO2 absorption and regeneration the capture of SO2 amounts to $8.4 MM
product pricing. In 2007, prices for system as identified as being contained annually. The project is a break-even
sulphur were in the $45/St ($50/metric in the battery limits in Figure 4. proposition if sulphur revenue is more
tonne) range. In late 2008, sulphur The ISBL costs for the regenerable SO2 than $520/St over the project life.
prices rose to as high as $630/St ($700/ scrubbing system amount to $42.0 MM
metric tonne). Sulphuric acid values and the annual operating cost is $14.6 Case study 2
have been similarly variable and have FCCU regen gas SO2 scrubbing
increased from $90/St ($100/metric FCCU SO2 scrubbing basis:
tonne) to as high as $329/St ($360/ SO2 cost and utility consumption Gas oil feed: 87 kbpd
metric tonne). It is widely expected that
table: cogen case Sulphur in feed: 2.4 wt%
by-product values will fall, but specific Resid feed rate, kbpd 15.0 Regen gas generated: 256 scfm
values are more difficult to predict. For Firing rate, MMBTU/hr 3402 Flue gas SO2 concentration: 2100 vppm
this discussion, it is assumed that sulphur MW equivalent 350 SO2 content of regen gas: 2.6 St/hr
prices will average $250/St for the next SO2 captured, St/hr 7.9 This scenario is based on the refinery
15 years. Annual sulphur equivalent, St/yr 34 602 generating up to 87 kbpd of catalytic
Flue gas flow rate, kscfm 884 feed from the crude charge of 250 000
Case study 1 Flue gas SO2, vppm 1833 bpd. If the sulphur content of the feed is
SO2 scrubbing in co-generation Capital cost, $MM1 42.0 2.4 wt% and 10% of this is carried in the
application Annual op cost, $MM2 14.6 coke to the catalyst regenerator, a total
Cogen firing basis: Annual by-product credit, $MM 8.4 of 2.6 St/hr of SO2 must be removed
Resid feed rate: 15 kbpd Net operating cost 6.2 from the regen gas.
Sulphur in feed: 3.6 wt% Particulate management in the FCCU
Utility consumption
Heating value: 17 100 Btu/lb fuel is critical because particulate emission
Power, kW-hr/tonne SO2 970
Total firing rate: 3402 MMBtu/hr — 350 concentrations can change quickly from
Steam, ‘000 lb/tonne SO2 23.3
MW equivalent at 9700 Btu/kW heat low concentrations (0.04 gr/scf of gas,
Cooling water, ‘000 gal/tonne SO2 234
rate. or 100 mg/Nm3) to several grains of
In this example, residuum is fired to a 1 Capital cost refers to inside battery limits particulate per standard cubic foot of
utility type boiler. Steam is raised to feed (ISBL) total installed costs for a high labour gas as a result of regenerator cyclone
power turbines and to supply steam to efficiency, low material cost location. Owner’s failure or catalyst flow reversal. A venturi
costs, incremental utility capital costs and
the refinery. Flue gas is directed to an prescrubbing device in the flue gas
overheads are not included. Costs are to be
air-to-air preheater and then to an considered as ball park estimates only, for the conditioning system can accommodate
electrostatic precipitator, where solids four cases identified. these swings in particulate content of
are removed. The cool gas flows to the 2 Operating costs are based on $3.63/’000lb for the flue gas.
prescrubbing system and then to the steam, $0.06/kWh for power and $0.08/’000 Unlike the cogen case, additional flue
gallons for cooling water. Operating and
SO2 scrubbing system. The overall flue maintenance costs are not included, but
gas cooling is required to ensure the gas
gas management systems are broken are typical for low corrosion, petrochemical enters the SO2 scrubber at a low enough
down into three discrete parts: applications. temperature for sufficient SO2 removal.
— The combustion system The specific steam consumption for
— The flue gas pretreatment system Table 1 the cogen case is higher than for the

www.eptq.com PTQ Q1 2009 129

www.ptqenquiry.com
for further information
 Prescrubber Amine purification Regenerator
unit (APU) O/H system
4O 325
Cat. regen. CO boiler Battery
limits 4O STACK
heat recovery
!05

ESP
#/
BOILER
Amine
absorber Regenerator

Cat.
!IR regen. ,0
3TEAM
&LY
ASH 7ASH (/

7ASTE (/
FCC catalyst Flue gas pretreatment SO2 management
regenerator 3/ REMOVAL n 3"37%30 3/ CAPTURE
$UST REMOVAL n $RY %30 3/ REGENERATION
1UENCHCOOL n 0RESCRUB

Figure 5 Process flow diagram: FCCU CO boiler flue gas DeSOx unit

FCCU case because the gas is not cooled, Tail gas SO2 concentration: 4500 vppm allows conversions of greater than 99.9%
and higher amine circulation and steam Recovered SO2: 12 St/day of the feed to sulphuric acid and is
flow rates are needed to be sure the gas Greater thermal processing and capable of meeting a sulphur emission
is treated to specification levels of SO2. hydrotreating of cracked products specification below 0.33lb sulphur per
The cooling water demand is greater for reduce the octane content of light tonne of acid produced. Further, the
the FCCU case to reflect the additional distillate streams. To maximise their integration of the system into the acid
cooling load in the prescrubber system. return on octane, the refiner will need plant design disconnects emission values
Table 2 shows that the ISBL TIC to consider upgrading their alkylation from catalyst performance and allows
capital cost of the regenerable SO2 system, resulting in the consumption lean Cansolv solvent to be sourced from
scrubbing system amounts to $20 MM of greater amounts of fresh acid and the a common refinery SO2 regeneration
and that the annual operating cost is generation of increasing volumes of system. Figure 6 illustrates the flow
estimated to be $5.7 MM. The price of spent acid. Incorporating an acid plant scheme used for a spent acid regeneration
sulphur must remain above $590/St to into the refinery process scheme reduces unit and its SO2 tail gas unit.
break even for this case. the reliance on outside contractors to Table 3 shows some of the
process spent acid and allows the performance characteristics for SO2
Case study 3 refiner to direct some of their by- scrubbing in a hypothetical 400 St/day
Spent acid regeneration product H2S or elemental sulphur to the H2SO4 spent acid facility.
Spent acid feed basis: acid plant and engage in what is now a Specific consumption rates of steam
Acid plant production rate: 400 St/d lucrative market for sulphuric acid by- and cooling water per tonne of SO2 are
Tail gas flow rate: 22 kscfm product. Alkylation units consume very much advantaged in this system
between 15lb and 20lb of acid per when compared to FCCU and cogen
Operating parameters for the FCCU barrel. Hence, a 200 St/day spent acid absorption because acid plant tail gas is
CO boiler flue gas DeSOx unit regeneration unit would be required to concentrated in SO2, contains no water,
satisfy the local requirements of the
FCCU feed rate, kbpd 87.5
alkylation unit. For this discussion, it is Operating parameters for
SO2 captured, St/hr 2.6
assumed that an additional 200 St/day the SAR DeSOx unit
SO2 captured, St/day 62.4
of acid can be sold to external customers
Annual sulphur equivalent, St/yr 11 388
to enhance the value proposition for Acid plant production, St/day H2SO4 400
Flue gas flow rate, kscfm 256
the project. SO2 captured, St/hr 0.5
Flue gas SO2, vppm 2100
Sulphuric acid plants are normally SO2 captured, St/day 12
Capital cost, $MM 20.0
configured as single absorption and Annual sulphur equivalent, St/yr 2200
Annual op cost, $MM 5.7
double absorption flow schemes. Single Flue gas flow rate, kscfm 22
By-product credit, $/t S 250
Flue gas SO2, vppm 4500
Annual by-product credit, $MM 2.9 absorption plants are generally regarded
Capital cost, $MM 4.7
Net operating cost, $MM 2.8 as being able to achieve in excess of 99%
Annual op cost, $MM 0.4
conversion with fresh catalyst, and
Utility consumption double absorption plants can achieve Utility consumption
Power, kW-hr/t SO2 1290 conversions in excess of 99.9%. Addition Power, kW-hr/t SO2 114
Steam, ‘000 lb/t SO2 17 of an absorption step essentially is Steam, ‘000 lb/t SO2 6.6
Cooling water, ‘000 gal/t SO2 510 considered to be an equivalent process Cooling water, ‘000 gal/t SO2 59
option to the use of a tail gas SO2 capture
and recycle flow scheme.
Table 2 The regenerable SO2 scrubbing system Table 3

www.eptq.com PTQ Q1 2009 131

 PROCESS INSIGHT
Selecting the Best Solvent for Gas Treating

Selecting the best amine/solvent for gas treating is not a trivial task. Tertiary Amines
There are a number of amines available to remove contaminants such A tertiary amine such as MDEA is often used to selectively remove
as CO2, H2S and organic sulfur compounds from sour gas streams. H2S, especially for cases with a high CO2 to H2S ratio in the sour gas.
The most commonly used amines are methanolamine (MEA), One benefit of selective absorption of H2S is a Claus feed rich in H2S.
diethanolamine (DEA), and methyldiethanolamine (MDEA). Other MDEA can remove H2S to 4 ppm while maintaining 2% or less CO2 in
amines include diglycolamine® (DGA), diisopropanolamine (DIPA), the treated gas using relatively less energy for regeneration than that
and triethanolamine (TEA). Mixtures of amines can also be used to for DEA. Higher weight percent amine and less CO2 absorbed results
customize or optimize the acid gas recovery. Temperature, pressure, in lower circulation rates as well. Typical solution strengths are 40-50
sour gas composition, and purity requirements for the treated gas weight % with a maximum rich loading of 0.55 mole/mole. Because
must all be considered when choosing the most appropriate amine for MDEA is not prone to degradation, corrosion is low and a reclaimer
a given application. is unnecessary. Operating pressure can range from atmospheric,
typical of tail gas treating units, to over 1,000 psia.
Mixed Solvents
In certain situations, the solvent can be “customized” to optimize the
sweetening process. For example, adding a primary or secondary
amine to MDEA can increase the rate of CO2 absorption without
compromising the advantages of MDEA. Another less obvious
application is adding MDEA to an existing DEA unit to increase the
effective weight % amine to absorb more acid gas without increasing
circulation rate or reboiler duty. Many plants utilize a mixture of amine
with physical solvents. SULFINOL is a licensed product from Shell Oil
Products that combines an amine with a physical solvent. Advantages
of this solvent are increased mercaptan pickup, lower regeneration
energy, and selectivity to H2S.

Primary Amines Choosing the Best Alternative

The primary amine MEA removes both CO2 and H2S from sour gas Given the wide variety of gas treating
and is effective at low pressure. Depending on the conditions, MEA options, a process simulator that can
can remove H2S to less than 4 ppmv while removing CO2 to less than accurately predict sweetening results is a
100 ppmv. MEA systems generally require a reclaimer to remove necessity when attempting to determine
degraded products from circulation. Typical solution strength ranges the best option. ProMax® has been proven
to accurately predict results for numerous
from 10 to 20 weight % with a maximum rich loading of 0.35 mole
process schemes. Additionally, ProMax
acid gas/mole MEA. DGA® is another primary amine that removes
can utilize a scenario tool to perform
CO2, H2S, COS, and mercaptans. Typical solution strengths are 50-
feasibility studies. The scenario tool may
60 weight %, which result in lower circulation rates and less energy
be used to systematically vary selected
required for stripping as compared with MEA. DGA also requires
parameters in an effort to determine the
reclaiming to remove the degradation products. optimum operating conditions and the appropriate solvent. These
Secondary Amines studies can determine rich loading, reboiler duty, acid gas content of
The secondary amine DEA removes both CO2 and H2S but generally the sweet gas, amine losses, required circulation rate, type of amine
requires higher pressure than MEA to meet overhead specifications. or physical solvent, weight percent of amine, and other parameters.
Because DEA is a weaker amine than MEA, it requires less energy for ProMax can model virtually any flow process or configuration
stripping. Typical solution strength ranges from 25 to 35 weight % with including multiple columns, liquid hydrocarbon treating, and split flow
a maximum rich loading of 0.35 mole/mole. DIPA is a secondary amine processes. In addition, ProMax can accurately model caustic treating
that exhibits some selectivity for H2S although it is not as pronounced applications as well as physical solvent sweetening with solvents such
as for tertiary amines. DIPA also removes COS. Solutions are low as Coastal AGR®, methanol, and NMP. For more information about
in corrosion and require relatively low energy for regeneration. The ProMax and its ability to determine the appropriate solvent for a given
most common applications for DIPA are in the ADIP® and SULFINOL® set of conditions, contact Bryan Research & Engineering.
processes.

www.ptqenquiry.com Bryan Research & Engineering, Inc.

for further information
P.O. Box 4747 • Bryan, Texas USA • 77805
979-776-5220 • www.bre.com • sales@bre.com
 Acid plant Acid plant Acid plant
burner reactor absorber
Spent Steam
H2SO4

98%
H2SO4
97.5%
Air
98% H2SO4
H2SO4
98%
H2SO4

SO2 Battery
recycle To stack limits
APU

Regenerator Quench H2O

Steam
Amine
absorber

Figure 6 Spent sulphuric acid unit flow sheet

requires no external cooling in the

prescrubber and is free of particulates. Comparative SRU performance at 376 St/d and 600 St/d
Furthermore, the elimination of a 376 St/day SRU 600 St/day SRU
circulated prescrubber in this design SRU configuration 3 stage 3 stage
avoids the need for a tail gas ID fan to Conversion, 100% of equil. 98.6% 99.1%
push tail gas through the SO2 scrubbing Acid gas feed 1100 lbmol/hr H2S 1254 lbmol/hr H2S
system. Rxn furnace comb. air 3000 lbmol/hr 2000 lbmol/hr
External SO2 to Rxn furnace 0 190 lbmol/hr (dry)
Impact on the SRU External SO2 to 1st stage Claus 0 120 lbmol/hr (dry)
The transition from the 2008 Combustion air 3000 lbmol/hr 2000 lbmol/hr
hypothetical refinery processing case to Rxn furnace temp 2635°F 2050°F
the 2028 case requires that the SRU be
modified to increase elemental sulphur
production from 376 St/d to 600 St/d. Table 4
This represents a 60% increase in SRU
capacity. The SRU design is greatly 2300°F, where NH2 is a component of t/day cases is 3900 lbmol/hr and 3400
defined by gas residence time and the SRU feed, or to keep conversion lbmol/hr respectively.
temperature considerations in the temperatures above 2000°F, where only The conclusion to be drawn from
reactor, and space velocity and sulphur hydrocarbons are present in the acid Table 4 is that the existing SRU reaction
rundown considerations in the sulphur gas. Acid gas and air preheat can be used furnace and reactors are sufficient to
condensers. to increase reaction furnace temperatures, handle increased sulphur loads in the
When air is used to oxidise the and part of the SO2 can be bypassed to future refinery if NH3 is not a feed
necessary amount of H2S to SO2 to the first Claus stage to prevent flame component of the SRU. It will be
satisfy the sulphur reaction, the air-to- cooling. This case was configured to important, however, that design checks
acid gas ratio needed to satisfy the O2 ensure the reaction furnace temperature of items such as sulphur condenser
demand amounts to 2.37 moles of air does not drop below 2000°F. duties, rundown and pump-out
per mole of H2S fed to the SRU. The Table 4 illustrates the operating capacities and the approach to the
introduction of air to the reaction conditions of a three-stage Claus SRU, sulphur dew point temperature in the
furnace introduces 1.87 moles of inert designed to produce 376 St/day of reactors be performed.
N2 per mole of H2S. If 60% more capacity sulphur and a 600 St/day unit that is fed
is required and the reaction furnace 310 lbmol/hr of externally sourced SO2. Case study 4
residence time must remain below a For the 376 t/day case, a total of 4100 SRU tail gas scrubbing
threshold level, then more than 60% of lbmol/hr of air and acid gas is fed to the In some cases, the upgrade of the refinery
the volume of reactants must be SRU reaction furnace. For the 600 t/day will require the addition of an SRU tail
eliminated from the reaction furnace case, a total of 3444 lbmol/hr of gas clean-up system. This can also be
feed. This can be accomplished by air and acid gas is fed to the SRU satisfied by the installation of a
eliminating N2 from the feed. reaction furnace. regenerable SO2 scrubber as part of the
The primary concern in SRU design is Similarly, the feed to the first-stage SRU expansion. Figure 7 shows how the
to ensure temperatures remain above Claus reactor for the 376 t/day and 600 Canslov tail gas system can be integrated

www.eptq.com PTQ Q1 2009 133

 4O STACK

Battery
limits
!MINE
PURIFICATION
UNIT

Amine
absorber
Regenerator

3/ REMOVAL

1UENCH COOLING -AKEUP 3TEAM

WATER

0URGE WATER TO WATER TREATMENT

3TEAM
&UEL 3TEAM 3TEAM 3TEAM 3TEAM

!CID GAS
(3 3/

Thermal Reaction
oxidiser furnace
!IR
!IR

3ULPHUR 3ULPHUR 3ULPHUR 3ULPHUR

Figure 7 SRU tail gas clean-up unit

Operating parameters for the SRU Non-regenerable SO2 scrubbing reagent requirements
unit: 97% conversion basis
Product Consumption, Equivalent Equivalent of case
SRU production, St/day sulphur 600 lb reagent per consumption/cost consumption/cost
SO2 captured, St/hr 1.5 lb of SO2 (St/d; $MM/yr) (St/d; $MM/yr)
SO2 captured, St/day 36.0 of reagent for reagent for FCCU
Annual sulphur equivalent, St/yr 6570 co-gen case 62 tpd SO2
Flue gas flow rate, kscfm 24 185 tpd SO2
Flue gas SO2, vppm 13 000 Calcium carbonate (limestone) 1.56 300/$3.2 MM 100/$1.2 MM
Capital cost, $MM 7.1 Calcium hydroxide (lime) 1.15 220/$7.9 MM 70/$2.6 MM
Annual op cost, $MM 1.2 Sodium hydroxide solid 1.25 240/$26.0 MM 80/$8.5 MM

Utility consumption
Power, kW-hr/t SO2 200
Table 6
Steam, ‘000 lb/t SO2 7.3
Cooling water, ‘000 gal/t SO2 220
Waste production/disposal
Table 5
lb dry waste Co-gen case FCCU case
material generated waste generated waste generated
into an existing three-stage SRU that is
(as SO4) per lb St/d; $MM/yr $MM/yr at $20
designed for a 97% conversion efficiency
of SO2 removed at $20 per tonne St/d; per tonne
at end of catalyst run conditions.
dry basis dry basis
Table 5 shows some of the performance Calcium carbonate 2.13 (solid waste) 403/$3.0 MM 132/$1.0 MM
characteristics of regenerable SO2 (limestone)
scrubbing in a hypothetical SRU that Calcium hydroxide 2.13 (solid waste) 403/$3.0 MM 132/$1.0 MM
operates at a sulphur rundown rate of (lime)
600 St/d. In this case, operating costs do Sodium hydroxide 2.22 (liquid waste) 419/$3.0 MM 137/$1.0 MM
not include natural gas consumption
and steam production in the tail gas
thermal oxidiser, which are outside of Table 7
the CTI scope.
Extensive flue gas cooling is required tonnes of water per tonne of SO2 Comparison to
to cool the gas to absorber conditions captured by the tail gas system. On an non-regenerable systems
and to remove the water formed from SRU basis, this translates to 0.4 tonnes By-product management
the Claus reaction. The prescrubbing of water per tonne of sulphur directed Non-regenerable SO2 scrubbing systems
system must purge 44 gpm, or 7.3 to the pit. in wide use today most often employ

134 PTQ Q1 2009 www.eptq.com

sodium hydroxide, lime (calcium oxide) and limestone
(calcium carbonate) as reagents to remove SO2 from flue gas
streams. Prices for reagents have varied greatly. NaOH has
ranged between $200/t and $800/t. Its supply is tied to
energy prices and markets for chlorine, a by-product of
NaOH. Lime has varied between $129/t and $170/t since
2006 and limestone has held steady at a cost of between
$10/t and $20/t at the quarry. Delivery costs are extra. The
delivered costs of NaOH, lime and limestone might average
$300/t, $100/t and $30/t for the purposes of this example.

Non-regenerable waste management

SO2 is absorbed as the sulphite or bisulphite of the sodium
or calcium salt. It must be oxidised to the sulphate
form of the salt in an air-blown contactor and discharged
to waste to minimise its chemical oxygen demand (COD).
As shown in Table 7, a tonne of SO2 generates over two
tonnes of waste (dry basis) when converted to the sulphate
of the salt.
Waste management costs represent a significant portion
of the overall operating cost for a non-regenerable SO2
scrubbing system.

Conclusions
Overall, regenerable SO2 scrubbing systems installed in four
locations of the refinery will capture 300 St/day of SO2 (150
St/day sulphur equivalent) that will balance the growing
load of H2S generated by the hydrotreaters. The addition of
both SO2 and H2S to the Claus plant feed will help avoid
major additional investment in sulphur recovery facilities.
A total of nearly $74 MM of capital is required to install
four SO2 capture and solvent regeneration systems in this
hypothetical 250 000 bpd refinery. Incremental annual
operating costs of $23 MM for the SO2 capture systems is
expected, but most of this cost will be offset by a by-product
revenue stream that will generate up to $14 MM annually.
The net operating cost for regenerable vs non-regenerable
solvents, inclusive of by-product revenues, is lower than that
for lime and sodium hydroxide-based non-regenerable
systems. It is greater than for limestone-based scrubbing
systems, if the delivered price of limestone is $30 per tonne
or if the average sulphur price over the life of the project
exceeds $250/t.
Capital cost savings can be obtained in this example. This
scenario has considered that four SO2 absorbers and
regenerators are required to satisfy this project and a
standalone island design concept has been considered. An
island concept is not essential to the design. Regenerable SO2
absorbers can be located remotely from the regenerator and
lean and rich DS piping can be run through the refinery to
serve each island. A common SO2 solvent regeneration
system, located adjacent to the H2S amine regenerator, SRU
and SAR areas, will allow the SRU and SAR to back each other
up as disposal points for either excess H2S or SO2 produced
by the refinery. The maturity of the system and its use in a
number of industries now allows the refinery to consider SO2
capture as simply another utility system. It can be applied on
a refinery-wide basis, much as is already done for H2S capture
systems.

References
1 Blume A M, Yeung T Y, Analysing economic viability for opportunity
crudes, PTQ, Q3 2008, 67–73.
2 Couch K A, Glavin J P, Johnson A O, UOP, Impact of bitumen feeds
on the FCCU: part 1, PTQ, Q3 2008, 23–28.
3 Energy Information Administration, World Crude Oil Prices,
http://tonto.eia.doe.gov/dnav/pet/pet_pri_wco_k_w.htm
4 Energy Information Administration, Crude Oil Input Qualities,
http://tonto.eia.doe.gov/dnav/pet/pet_pnp_crq_dcu_nus_m.htm

Rick W Birnbaum is Sales Manager for Cansolv Technologies in

Montreal. Email: rick.birnbaum@cansolv.com

www.ptqenquiry.com
www.eptq.com for further information
PTQ Q1 2009 135
 PARIS, FRANCE, 10-12 MARCH 2009

THE EUROPEAN
FUELS CONFERENCE
10TH ANNIVERSARY MEETING

KEY SPEAKERS
Jean-Jacques Mosconi, Senior Vice President, Strategy and Development, TOTAL
Aileen Jamieson, Managing Consultant, WOOD MACKENZIE
Fatih Birol, Chief Economist, INTERNATIONAL ENERGY AGENCY
Nancy Young, Vice President Environment Affairs, INTERNATIONAL AIRLINES ASSOCIATION
Capt Nicholas Mahony, Marine Manager, BIMCO
Raffaele Liberali, Director for Technology, EUROPEAN COMMISSION
Gijs Vriesman, Chair, EUROPEAN INDUSTRY GROUPING FOR A FUEL CELL AND
HYDROGEN JOINT TECHNOLOGY INITIATIVE (NEW IG)
Jean François Gruson, Head of Economy Department, INSTITUT FRANCAIS DU PETROLE

Only at the European Fuels conference will you hear cross-industry perspectives at
unique streamed sessions covering Automotive, Aviation and Marine and Bunker
fuels allowing you to delve into the challenges relevant to your own industry
Receive a global overview of the fuels industry from strategic visionaries who will
deliver cutting edge case studies helping you to keep abreast of your competitors.
THE ALTERNATIVE FUELS SYMPOSIUM is your chance to listen to the most relevant
issues from fuel and engine developers
Seize this opportunity to network and influence over 250 major refiners and fuel
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JOIN co-hosts TOTAL during the 10th Anniversary celebration reception where you
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EVENT CO-HOST: SPONSOR:

 and Petrochemicals Limited, Kochi
INDUSTRY NEWS Refineries, HPCL and IOC, will together
add some 286 000 b/d of capacity
by 2012.
Tough decisions for refining This large project proceeded in the face Not all projects have had a smooth
industry players of equipment shortages and cost start. IOC, facing a near-doubling of
With the golden age of record high escalations big enough to result in expenditure on its Paradip refinery from
margins and high oil products demand project cancellations for even the most the Rupees 256.5 billion ($5.98 billion)
behind it, the refining industry has profitable oil and refining companies. spending its board had approved in
some complicated decision-making With benchmark crude futures principle, has scrambled to look at all
ahead of it, said Booz & Company in a slipping from a historic high above available options to finance the project
recent report. The analysis was published $147/barrel in July 2008 to below $55/ off balance sheet. The options include
before oil prices swung below the barrel in late November 2008, the scaling down the project size and
psychologically important $100/barrel refining industry is now viewed as being implementing it in stages. The
mark as the September 2008 bankruptcy on the cusp of a sharp downturn after configuration currently on the drawing
of Wall Street giant Lehman Brothers sustained high downstream margins board is a 300 000 bpd refinery and a
unleashed a global financial tsunami. It from 2003–2007. The likely contraction petrochemical complex including
said uncertainties facing the refining in global oil demand growth in the paraxylene and purified terephthalic
sector included the effect of prices on oil coming months, far outpacing any acid (TPA) production facilities.
demand, the extent to which new increase in Chinese demand, coupled An important factor detrimental to
transportation technologies will displace with more than half a million bpd of future profitability for Indian refiners is
oil-based vehicles, the cost of building new capacity at the Reliance Jamnagar that the Indian government will no
new refining capacity and the future complex, is expected to exacerbate a longer extend a seven-year tax holiday
level of biofuel use amid growing drop in refining margins across Asia. (“sunset clause”) to new refinery projects
concerns about food prices. Reliance was already operating an commissioned after March 2012. This
As the global economy deflates, export-oriented 660 000 b/d refinery at income tax holiday to refineries will be
refining margins could worsen to $3–5/ Jamnagar. available before March 2012 only if they
barrel, levels not seen since 2002, Apparently, Reliance and other Indian are owned by a public sector company
according to the study. Over the longer refiners are continuing to proceed with or built by companies where state-run
term, beyond 2013, the strength of new refinery projects and capacity firms have a 49% stake. These conditions
refining margins will be dictated by expansions. These expansions, which have kept refineries planned by Essar Oil
demand growth in the developing world would seem to contradict the current at Vadinar in Gujarat, Nagarjuna Oil at
— a fundamental shift from dynamics of business climate, are in keeping with the Cuddalore in Tamil Nadu and Cals
the recent past, when margin cycles Indian government’s plan to make the Refineries at Haldia in West Bengal out
were determined almost solely by the country a refining hub, in response to of the tax benefit, as they have no public
speed at which capacity was added, Booz the expected long-term global shortage sector equity. Sources said even though
& Company said. As fuel demand shrinks of refining capacity. To be sure, the long- work on private sector refineries began
and refining capacity expands, refiners term outlook held by many planners in much before the sunset clause was
could find themselves in an oversupply developing countries (including those in introduced, the Finance Ministry has
situation. Most strikingly, the US could Africa and Venezuela) is for refined ignored their cause.
soon become a net exporter of gasoline product demand to increase steadily in Essar, which is expanding its 10.5
— something that seemed highly spite of the current surplus in refining million tonnes Vadinar refinery to 34
unlikely just a few months ago. Asia capacity (and dramatic declines in million tonnes, has written to Prime
could mop up the surplus, but the effect refining margins). For example, Bharat Minister Manmohan Singh, saying the
of such a shift, given shipping costs and Oman Refineries, a joint venture between move would severely affect the viability
specific refining economics, would be to state-owned refiner Bharat Petroleum of the project and its financial interest
reduce margins for both European and Corporation Limited (BPCL) and Oman would be jeopardised. The Vadinar
US refiners, Booz & Company warned. Oil Corporation, is progressing with a expansion is to be completed before the
The growing importance of biofuels, 120 000 bpd refinery at Bina in Madhya public sector refineries come on-stream.
with more countries mandating spiking Pradesh and targeting completion for “This will make it impossible for our
transportation fuels with the cleaner the end of 2009. refinery to compete with Paradeep, Bina
product, is another ingredient on the Hindustan Petroleum Corporation or Bhatinda refineries, as well as other
supply-side equation. However, the Limited has a 180 000 bpd refinery existing refineries, as both refineries in
enduring truth for refiners globally is project at Bhatinda in the northern state the past and also the upcoming refineries
that they work in a cyclical industry, of Punjab, aimed for completion in being built will enjoy this benefit (sunset
their investment decisions target a span 2011. The largest state-owned refiner clause), whereas Essar Oil will not be
of two to three decades rather than a and marketer, Indian Oil Corporation treated at par,” the company wrote to
couple of years and, irrespective of the (IOC), is working on a 300 000 bpd the Prime Minister. “It is very unfortunate
depth and length of the looming refinery at Paradip on the country’s east that the proposed amendment would be
downturn, when the world is back on its coast. The project had been targeted for discriminatory to private sector refineries
feet financially oil products demand completion by fiscal 2011–2012, but is and will make private sector investments
could once again quickly outpace now at a crossroads over costs. inviable,” it said seeking a level playing
production capacity. Essar Oil, the only other private field by removing the inequality.
refiner, has the most aggressive capacity Nagarjuna Oil is building a six million
Asian refining projects expansion plans. It is more than tripling tonnes refinery in Tamil Nadu, while
In spite of the rapid spread of the global its relatively new 210 000 bpd refinery at Cals Refineries is assembling a five
financial crisis, Reliance Industries in Vadinar on India’s west coast to 680 000 million tonnes unit in West Bengal.
India committed in late 2008 to proceed bpd by 2010. Other expansions and In any event, Platts estimates that if
with pre-commissioning at the 580 000 debottlenecking plans at existing all the current capacity expansions and
bpd export-oriented refining complex. refineries, including Mangalore Refinery new refinery projects in India proceed

www.eptq.com PTQ Q1 2009 137

without a hitch, the country’s refining greenfield refinery and petrochemical 240 000 bpd refinery at Quanzhou on
capacity will rise 65% from the current complex including an 800 000 mt/year the coast of Fujian province, which is
3.0 million bpd to almost 4.93 million ethylene plant and downstream facilities expected to be ready in 2010.
bpd by 2012, well beyond the rise in at Pengzhou in the southwestern This does not take into account the
domestic demand. The surplus refining province of Sichuan. Guangdong possibility of further downward revisions
capacity, which will rely on export province alone, the economic in world oil demand growth estimates.
markets globally, will grow from about powerhouse of China, has set a goal to The Paris-based energy policy adviser to
580 000 bpd in 2008 to 2.09 million bpd raise its crude refining capacity to 2 the industrialised world is still waiting
by 2012, according to Platts’ million bpd and ethylene production to see if a prolonged economic downturn
calculations. capacity to more than 4 million mt/year in the US might signal a monumental
Alliances between Indian refiners and by 2012. The province currently has a structural shift in US oil demand and
Middle Eastern oil producers are being refining capacity of 670 000 bpd. has kept its forecasts for China, India
considered. For example, Saudi Aramco The four major state giants in China and the Middle East stable, saying
has not made any investments in India. — Sinopec, PetroChina, Sinochem and statistically there is no evidence of a
Its President and CEO, Abdallah S CNOOC — are together expected to add slowdown in these regions. However,
Jum’ah, said that inter-dependence is a some 113.8 million mt/year (about 2.276 the IEA’s Executive Director Nobuo
point of strength rather than a sign of million bpd) of refining capacity over Tanaka acknowledged the biggest
weakness. Saudi Aramco and Saudi 2006–2010, taking the country’s total to question mark was how the oil demand
Arabia are continuing to work hand-in- around 9.4 million bpd, according to of China, India and countries in the
hand with the Indian petroleum sector. data from Sinopec. Altogether, Asia is Middle East might get affected by the
Oil already accounts for more than 35% expected to add about 1.4 million bpd global financial turmoil. At the end of
of India’s primary energy consumption of annualised new refining capacity in the day, Asian refiners can take comfort
and is set to grow in both absolute and large projects by the end of 2009, in from the fact that they are in the hub of
percentage terms, and because India’s addition to the 700 000 bpd added in the global centres for future oil demand
own petroleum reserves are limited that 2008. According to data provided by growth, and their billion-dollar
means a growing reliance on oil Credit Suisse, the large new plants in investments are going into facilities
imports. China and India will have an average capable of taking in the trashiest crudes
In fact, the IEA forecasts India’s distillate yield of 35–45%. — sour, heavy, and even highly acidic
petroleum imports to triple between The capacity addition from new — to churn out the cleanest of products.
now and 2030, at which point India refineries in Asia alone matches the In short, they are well positioned to ride
will be the world’s third largest importer International Energy Agency’s latest the next wave of Asian oil demand
of petroleum, with volumes roughly pared-down estimates for a 700 000 b/d growth and attractive margins, whenever
equivalent to Japan’s current imports. growth in global oil demand for 2008 it comes.
Reliance Industries’ Company Chairman, and well exceeds the 800 000 b/d figure
Mukesh Ambani, recently noted the agency projects for increase in 2009 European refiners cutting back
that a stable oil pricing regime was world consumption. on production
needed to sustain investments and Chinese oil companies are also Europe’s oil refiners may have to curtail
economic growth. He said that: “When becoming very active overseas as they production in early 2009 as profit
in 1999 we started our first refinery at strive to keep their refineries supplied margins sag and worsening economic
Jamnagar, we saw a recession globally with feedstocks. The China-Russia $25 conditions curtail demand, according to
and when we are about to start up our billion loan for oil negotiation was a analysts and industry participants.
second refinery (at Jamnagar), history is work in progress as of late 2008. A CNPC While crude prices have more than
repeating itself.” source close to the negotiation noted halved since July this year, the rate of
In neighbouring China, state-owned that the two sides could eventually sign decline has been outpaced by drops in
integrated giant Sinopec in mid-2008 a contract. According to the agreement, the prices of refined products, most
launched operations at a 200 000 bpd Russia will contract to export 300 million noticeably for gasoline, as consumer
greenfield refinery at Qingdao on the tonnes of crude oil to China over the appetites slow down and Europe tilts
coast of the northern Shandong next 20 years. In other overseas activities, toward recession.
province. Two more major greenfield CNOOC has been bidding $300–$700 It has left refiners with the prospect of
refineries were due to be commissioned million for natural gas assets in the their refining margins turning negative
by early 2009. China National Offshore Caribbean area, and CNPC is expected in some instances, threatening a possible
Oil Corporation (CNOOC) will bring to take a 25% stake in the Pars LNG wave of discretionary run cuts and even
on-stream its 240 000 bpd Huizhou project in Iran. plant closures. “We forecast that
refinery at Daya Bay on the east coast of Middle Eastern national oil companies European refining margins will decline
the southern Guangdong province. The have also become quite active in China, sharply in 2009, driven by a much
state-owned upstream major is said not just to secure a market for their weaker supply/demand balance,
to be planning to invest in another crudes, but also to extend themselves especially for diesel, the key product for
$6.6 billion to expand the new further down the value chain. Kuwait European refiners,” said Neil McMahon,
Huizhou refinery to 440 000 bpd capacity Petroleum International and Sinopec, Senior Analyst at Bernstein Research in
by 2011. along with other partners, are planning London. Signs of reduced refinery runs
Sinopec announced plans in 2008 to a 300 000 bpd refinery that would have already started to emerge. Europe’s
expand its Maoming refinery in exclusively process Kuwaiti crude and a largest independent refiner, Petroplus
Guangdong from its current 270 000 1 million mt/year ethylene cracker at Holdings AG (PPHN.VX), has reduced
bpd capacity to 510 000 bpd, although Nansha in Guangdong. However, project run rates at its 117 000 bpd refinery in
the timeframe has not been disclosed. costs for this venture have ballooned to Teesside in the UK.
Sinopec and its foreign partners an estimated $8–9 billion in November Meanwhile, an official from French
ExxonMobil and Saudi Aramco intend 2008 from the $5 billion expected in union Confédération Générale du
to triple the current capacity of their December 2007, and the start-up Travail, or CGT, said that French oil
240 000 bpd refinery in Quanzhou, timeline is seen slipping to 2011 from major Total SA (TOT) may pare back its
which will process Saudi crude. the original 2010. KPI, in partnership gasoline production capacity in Europe
PetroChina is developing a 200 000 bpd with Sinochem and Shell, is building a amid what it sees as an irreversible

138 PTQ Q1 2009 www.eptq.com

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decline in demand from the US, Europe’s achieved without a revival in consumer could send prices at the pump up again
main export market, where the appetite demand. If production cuts succeed in after a significant recent drop.
for gasoline has also wilted in the lifting oil prices, without a commensurate However, several major refinery
tougher economic conditions. revival in product demand, refiners’ projects are moving forward and are
While the demand picture is already battered margins are likely to unlikely to be affected by the downturn.
challenging enough, Europe’s refiners worsen further. That raises the prospect They include Marathon’s 180 000 bpd
risk having to compete against a of more run cuts, more closures and, expansion of its Garyville, Louisiana,
potential surge in supplies from new worryingly for OPEC, even less appetite plant, targeted for completion in late
facilities, particularly in Asia and the for crude. 2009, and Motiva’s 325 000 bpd addition
Middle East, which are likely to heap to its Port Arthur, Texas, refinery, to be
pressure on refining margins. Energy North American refiners completed in 2011. Projects in earlier
consultancy Wood Mackenzie estimates delaying projects stages of development or still awaiting
an additional 12 million bpd of refining Irving Oil in Canada says it will stretch final investment decisions may be at
capacity will come online by 2015. out construction of its proposed second more risk.
Inventories will be increased by oil refinery for Saint John over an eight- In recent years, refiners announced
Reliance Industries’ 580 000 bpd year period rather than four years. Kevin aggressive plans to expand and upgrade
Jamnagar refinery in India. The refinery’s Scott, Senior Executive in charge of refineries as profits rose and global
diesel export capacity amounts to building the refinery, said that the demand for petroleum products such as
around 30% of current European project, now estimated to cost $8 billion gasoline and diesel fuel grew more
imports. “Our analysis suggests Europe as of late 2008, would still begin in quickly than the capacity to produce
will be the most attractive destination 2011, but will take longer to build up to them. In the US, refineries had been
for these cargoes,” McMahon said. “If full planned production levels of running near capacity, particularly
you are in Europe doing gasoline, it is 300 000 bpd. He says that is due to during peak summer demand periods,
not going to be pleasant,” said Alan shortages of skilled labour, higher costs so additions were viewed as safe, despite
Gelder, Vice President of downstream oil of capital and an expected downturn in the huge investment required. But the
at Wood Mackenzie consultancy. “It is the North American economy. gasoline market has weakened recently
not a particularly buoyant story for the The refinery is a mainstay in the because of increasing supplies and
refining sector.” Liberal government’s plans to create an shrinking demand.
European and Japanese non-integrated energy powerhouse in Saint John, and On the supply side, increased blending
refiners are most vulnerable to plant there have been projections it will of ethanol with gasoline means a gallon
closures, Fereidun Fesharaki, Chairman eventually create about 1100 full-time of gas stretches to more than a gallon of
and Chief Executive Officer of FACTS jobs. However, Energy Minister Jack Keir motor fuel. And more imported gasoline
Global Energy consultancy, said at a says he considers the announcement is available because Europeans are
recent conference in London. “The good news because he was fearful the switching to diesel vehicles. Finally,
global refining industry is headed company and partner BP might cancel refinery upgrades boost the amount of
towards substantial overcapacity,” the project entirely due to the economic gasoline that can be squeezed from a
Fesharaki added. downturn. Scott says the decision is barrel of crude. Meanwhile, US gasoline
Refinery utilisation in the member partly because the oil industry is facing demand has dropped 3% amid a slowing
countries of the Organization for some exceptional challenges, such as economy and $4 gasoline prices in
Economic Cooperation and Develop- rising capital costs and the dampening summer 2008. If the trend holds, it
ment (OECD) fell to an average of 78.9% in demand for petroleum products. would be the first time in more than a
in September, the lowest average level A recent pullback in plans to expand decade that demand has not increased
since October 1995, according to the or upgrade US oil refineries is an over the previous year.
group’s energy watchdog, the indication of the uncertainty facing Declining demand has been a major
International Energy Agency (IEA). refining companies after enjoying high factor in refiner decisions to delay or
European refinery utilisation stood at profits for several years. The uncertainty cancel projects, said Cindy Schild,
84.1% in September, the latest month stems from volatility in commodity Refining Issues Manager at the American
for which IEA data are available, and capital markets, as well as from a Petroleum Institute in Washington. But
compared with the 87.7% average since historic decline in gasoline usage she said there is still a case to be made
January 1995. beginning in 2008 that has raised doubts for more refining capacity. One reason is
But the travails facing Europe’s refiners over long-term demand for petroleum- greater flexibility to supply the nation’s
could equally translate into a headache based fuels. fuel needs because the US now imports
for the world’s key oil producers. “Oil Marathon Oil and Valero Energy had more crude than it has refining capacity,
consumption will not grow and may already announced by mid-2008 they she said.
even shrink,” warned Petroplus would delay or cancel refinery upgrades Today, US refining capacity stands at
Chairman Thomas O’Malley. OPEC is as part of broader cuts to capital spending about 17.8 million bpd over 150
expected to scale back oil production to programmes in 2009. And given current refineries, more than half of which are
prevent oversupplying market inventory economic difficulties, experts warn other on the Gulf Coast. The US consumes 20
levels. “In normal market conditions, projects could follow. “I think it is a million bpd of crude oil. Expansion
refinery cutting runs would translate trend you are going to see until at least projects in the pipeline today will add
into a build of crude stocks, but with the 2009, and it will continue beyond then about 900 000 bpd of crude distillation
run for cash there is no strong desire to if refining margins do not improve,” capacity by 2014, said Joanne Shore,
hold up stocks, so there is little choice said Brian Youngberg, Energy Analyst Analyst with the US Energy Information
but for OPEC to match any refinery run with Edward Jones in St Louis. As Administration. That is roughly in line
cuts with the corresponding production recently as summer of 2007, margins with the pace of additions over the past
cuts,” said Olivier Jakob, Managing were near $30 per barrel. They fell by decade, but lower than the 1.5 million
Director of Switzerland-based half in summer 2008 as oil prices bpd or more refiners had planned to add
consultancy Petromatrix. While skyrocketed and demand weakened. A a couple of years ago, she said. If all
restricting crude oil and refinery refining slowdown in the short term projects on the books now are completed,
production should in theory lead to a mostly would affect the industry and its the US will no longer need to add more
recovery in prices, neither will be employees, but a prolonged reversal refining capacity, the Energy Information

140 PTQ Q1 2009 www.eptq.com

Administration recently forecast. “You there is no stopping them. Africa’s Arabia is tentatively planning to build
are basically going to have enough existing LNG export capacity of 57.5 two 400 000 bpd export refineries —
capacity at that point,” Shore said. Even million t/y will increase by 28% (16.1 Jubail and Yanbu — in addition to the
before the economic downturn began in million t/y) by 2012 from projects already PetroRabigh refining (368 000 bpd) and
Q3 2008, the number of refinery projects going ahead, and by an additional 44.9 petrochemicals (2.4 million t/y).
started slipping partly because of rising million t/y by 2014 from projects still Three refinery projects in Saudi Arabia
labour and material costs, but has subject to final investment decisions.” have been delayed, according to the
accelerated recently and could fall The five African LNG exporters — Middle East Economic Survey (MEES).
further still, she said. For example, Algeria, Nigeria, Egypt, Equatorial Saudi Aramco and Dow Chemical’s joint
Houston-based Marathon Oil is delaying Guinea and Libya — all have projects for expansion of the Ras Tanura complex
a $1.9 billion upgrade of its 100 000 bpd new capacity either under construction faces delays because the project is
refinery in Detroit. Marathon had or in planning. In 2012, they will be believed to be too large for contractor
already decided earlier not to pursue joined by Angola, which also has KBR and needs to be divided with
other projects, such as two heavy oil additional capacity planned. Mauritania another company, MEES reported.
projects at its oil refineries in Robinson, and other countries are trying to According to earlier statements by
Illinois, and Catlettsburg, Kentucky, that prove up sufficient gas reserves to join officials, it had been expected that the
were deemed too costly. San Antonio- the club. expansion would be operational in Q1
based Valero, the nation’s largest refiner, To meet future LNG demand cost- 2012. The expected cost of the project is
is indefinitely postponing or delaying effectively, the world’s first unit believed to be around $8 billion. Bids for
expansions and upgrades at plants in employing floating liquefaction investment in the Jazan facility have
Port Arthur, Texas; Memphis, Tennessee; technology was ordered in September been delayed by nearly a year to March
St Charles, Louisiana; and Quebec. 2008. First announced in 2004, the Gulf 2009 while an incentives package is
The downturn has not been limited LNG Clean Energy Project on the prepared, MEES said.
to the US: Houston-based ConocoPhillips Pascagoula Bayou ship channel in The start-up of a plant to be operated
and the state-run Saudi Arabian Oil Co Pascagoula, Mississippi, is estimated to by Rabigh Refining & Petrochemicals
are delaying plans to build a 400 000 cost $1.1 billion. Technip performed the will probably be pushed back to Q1
bpd refinery in Yanbu, Saudi Arabia, FEED work for the project. Owned by 2009, MEES said. Saudi Arabia, the
citing uncertainties in the financial and partners El Paso Corp (50%), Crest Group world’s largest oil producer, is planning
contracting markets. (30%) and Angolan national oil company to raise refining capacity by 50% to
Sonangol (20%), the Gulf LNG Clean provide fuel oil and gasoline for soaring
LNG supply crunch Energy Project is expected to start up in local demand, and benefit from
An LNG supply crunch looks inevitable November 2011. Development of the exporting high-value oil products.
around 2011/13, but what about the project requires the construction of an
years beyond? Following the large unloading dock for LNG tankers (with 2009 light olefins analysis
increase in new LNG supply due to the option to easily add another dock in The massive build-up of ethylene
come on-stream by 2011 — around half the future). Aker Kvaerner has been capacity in the Middle East and Asia
in Qatar — incremental supply growth awarded the development contract. progressing at a rapid pace and is sending
will slow drastically for at least two Current plans envision the facility the industry into another down cycle.
years, according to IEA estimates. It welcoming a ship every three days for From 1995–2008, ethylene capacity
takes between three and four years from LNG unloading with a send-out capacity increased by more than 22 million
final investment decision (FID) to of 1.3 Bcf/d. metric tonnes in Asia/Pacific, and by
construct an export project. So, assuming Peru LNG is developing an LNG more than 13 million tonnes in the
projects are not unexpectedly delayed, it project consisting of the development, Middle East. By 2015, these regions are
is a straightforward matter to project the construction and operation of an LNG projected to add an additional 41 million
evolution of incremental supply up to plant. The plant consists of a 4.45 metric tonnes of ethylene capacity. With
four years ahead. But only five FIDs have million tonnes per annum liquefaction a significant cost-advantaged feedstock
been taken since the start of 2006, train. The LNG will be loaded onto base, ethylene production in the Middle
representing just 19 million tonnes a tankers at a marine loading terminal East will rank as the most competitive in
year (t/y) of new supply. adjacent to the LNG plant for export to the world. Given that the vast majority
How long this supply crunch will last market. Ex-Im Bank approved financing of this production targets export markets,
will depend on how many projects are for the project in early 2008. this surge in supply will dramatically
sanctioned over coming years. But while change trade dynamics. Ethylene and
the list of proposed projects is long, Middle Eastern projects derivative capacity investments in Asia
those with a realistic chance of coming As refining projects across much of the are primarily driven by the region’s
on-stream in the 2012–15 time frame Middle East come under threat from strong desire to be more self-sufficient in
are few, considering the current global cost inflation, Saudi Arabia seems petrochemical building blocks and
financial crisis. determined to push ahead with large supply the rapidly growing consumer
Africa’s LNG export capacity — already capacity additions. Current proposals goods manufacturing base operations.
more than a quarter of the world total would add some nine million bpd of The interplay between these somewhat
— could double over the coming five refining capacity through a combination conflicting strategies in Asia/Pacific and
years, with more to come after that if of plant expansions and new projects. the Middle East will invariably create
plans under discussion are realised. In But severe cost inflation means that not dynamic conditions in the global
addition to the current financial all of them will go ahead. Across the ethylene and derivatives markets. CMAI
downturn, the main brakes on region, expenditure planned for refining experts forecast that near-term crude oil
development are construction costs and, projects dwarfs upstream spending and natural gas values could help North
in Nigeria, security concerns. LNG budgets. According to estimates by Saudi America olefin derivative units remain
Analyst, Martin Quinlan, noted that: Arabia-based energy finance group competitive in the global market. From
“Algeria was the world’s first LNG Apicorp, total investments in the oil the mid-1990s to the early years of the
exporter, but it was many years before downstream for the 2008–12 period current decade, the international market
Africa’s other big gas countries were in a amount to $105 billion compared with share of North American ethylene
position to join the trade. Now, however, $67 billion for upstream ventures. Saudi derivatives was on the decline.

www.eptq.com PTQ Q1 2009 141

 vessels to efficiently and precisely heat
NEW PRODUCTS liquids and gasses in a variety of process
industries, including petrochemical, oil
and gas, as well as alternative fuels.
Chromalox has redesigned the heating
Calculating boiler wall thickness Rosemount 3051S pressure transmitter, element layout, bussing and housing on
with wireless technology is providing redundancy for an existing the new line of heaters to achieve more
The Smart Wireless technology from wired device that provides a critical even heat distribution, improved fluid
Emerson Process Management is measurement in the plant. This flow, and easier installation and service.
helping to provide valuable condition transmitter also reinforces the wireless This global design also streamlines
monitoring information at the Total mesh and provides an additional path manufacturing processes to increase
Petrochemicals plant in Carling Saint- back to the gateway. production flexibility and reduce
Avold, France. The introduction of The Smart Wireless’ self-organising turnaround times. Features of the new
wireless transmitters provides new mesh technology is very reliable, and product line include:
temperature measurement data, each measurement point has a — Octobox housing design: The
enabling the company to calculate redundant communication via two or Octobox design offers maximum
changes over time in wall thickness on three routes. With this technology, each flexibility for wiring options. It works
a boiler that provides steam to a steam wireless device can act as a router for with both NPT and Gland Plate Style
cracker, enabling personnel to anticipate other nearby devices, passing messages connectors, has six different angles to
when it may need replacement. along until they reach their destination. bring conduit into the housing, and the
By installing a wireless solution to If there is an obstruction, transmissions removable plate design allows the
connect the additional measurement are simply rerouted along the network installer to choose the exact connection
points, Total Petrochemicals removed until a clear path to the Smart Wireless size needed to match the conduit runs.
the need to install around 1km of new Gateway is found. As conditions change The housing is fully removable,
wiring. An additional benefit of the or new obstacles are encountered in a providing unrestricted access to the
solution has been a reduction in the plant, such as temporary scaffolding, bussing arrangement, thermowell and
movement of personnel into and new equipment or a parked construction circuit identification
around at-risk areas. trailer, these wireless networks simply — Triangular element pattern: The
Total Petrochemicals wanted to better reorganise and find a way to get their heating element pattern has been
understand the condition of the boiler signals through. completely redesigned to achieve more
and anticipate when it might need to be All of this happens automatically, even heat distribution, resulting in
replaced. To achieve this aim, the without any involvement by the user, cooler elements, fewer pressure drops
company was keen to introduce a providing redundant communication and a longer life for the unit
number of new temperature paths and better reliability than direct, — Element bussing/power connect-
measurement points. By measuring the line-of-sight communications between ions: A new style of vertical bussing is
internal and external temperature of the individual devices and a receiver. This used that simplifies installation while
boiler walls and identifying heat loss, it self-organising technology optimises providing more robust configuration to
is possible to calculate the material’s data reliability while minimising power support higher amperage, stronger
resistance and infer its thickness. “Our consumption. It also reduces the effort power connection points and cooler
plant is more than 30 years old,” said and infrastructure necessary to set up a bussing temperatures
Jerome Uszes, Electricity Control & successful wireless network. — Fully configurable: The new design
Regulation Maintenance Manager, Total jerry.moon@emerson.com is driven by the Chromalox
Petrochemicals. “With the rising cost of Configurator, which can reduce
copper and ageing existing wiring Flanges and circulation heaters engineering time by more than 90%.
(corrosion, infiltration and degradation Chromalox, a manufacturer of electrical This means that, in most cases, a custom
of armature), finding alternative heat and control products, has design will reach the production floor
methods to carry data throughout the introduced a new line of ANSI flange the same day it is ordered.
plant is becoming essential.” and circulation heaters with a Barbara.lee@chromalox.com
Eight Rosemount 648 wireless standardised design that meets all major
temperature transmitters were installed global certifications, eliminating the Detecting LPG gas hazards
directly onto the exterior of a boiler need for global organisations to deploy The Xgard IR LPG from Crowcon is a
drum situated 50m above the ground. different designs in different parts of low-cost infrared (IR) fixed gas detector
An Emerson Smart Wireless Gateway the world. The new line of immersion designed to detect liquid petroleum gas
was positioned on the roof of a technical heaters also features a number of (LPG) hazards before concentrations
building around 300m from the devices. enhancements that increase product reach flammable levels. Typical
Two additional temperature gauges functionality and performance. The environments requiring LPG monitor-
were installed in strategic areas between flange and circulation heaters are ing include petroleum refineries, petrol
the boiler and the gateway to provide designed to be mounted in pipes or stations, buildings that use LPG as their
sufficient coverage to the area and to main gas supply and many
enable supplementary measuring points manufacturing processes. Conventional
to be added in the future, as required. “By measuring the internal LPG detectors based on catalytic
Data from the wireless transmitters is and external temperature pellistors are susceptible to poisoning
passed from the Gateway to a third- in some industrial atmospheres. This
party DCS system via Modbus. From of the boiler walls and can make their readings unreliable and
the control room, the operators have identifying heat loss, it is even destroy the sensor altogether. The
gained visibility of the thermal status of Xgard IR LPG is totally immune to
the boiler walls, allowing them to possible to calculate the poisoning and will warn of LPG gas
determine how the internal (process) material’s resistance and hazards in environments that are
and external (climatic) conditions unsuitable for other types of sensors.
impact on the material’s deterioration. infer its thickness” The detection range is 0–100% of the
An additional wireless device, a lower explosive limit.

142 PTQ Q1 2009 www.eptq.com

 Infrared sensing has additional heater for transmission XRD between
benefits over traditional sensing. Unlike 25°C and 1000°C. Conversion between
catalytic pellistors, IR sensors detect “IR sensors detect standard geometry for flat samples and
flammable gas in inert backgrounds flammable gas in inert the capillary setup can be carried out in
and are not damaged by high gas minutes without removing the oven
concentrations. The Xgard IR consumes backgrounds and are not chamber from the goniometer.
half the power of comparable catalytic damaged by high gas Temperature data are saved in XRDML
bead detectors. The new IR LPG sensor format for further processing using
can be specified with two types of concentrations” PANalytical’s X’Pert Data Collector
enclosures: polyester-coated aluminium software, which controls all
or 316 stainless steel for maximum measurement routines.
corrosion resistance in extreme Studying materials in non-ambient
environments. The sensor, which has a Determination of conditions is important for many
life expectancy of over five years, is a biodiesel content industries and areas of research. XRD of
simple plug-in module that makes A new method that allows for the fast capillary samples offers an effective
replacement quick and easy. UL and accurate determination of biodiesel solution for preferred orientation
approved for use in hazardous areas to content in diesel from Grabner problems, providing an easy and rapid
detect methane, butane and propane, Instruments is used in IROX Diesel, a method for obtaining randomly
the Xgard IR LPG is Exd flameproof portable, fully automatic and extremely oriented powder samples. Uniform high
rated. The standard junction box is compact mid-FTIR spectrometer. The temperature performance and excellent
designed for both wall and ceiling instrument’s spectrometer is fine-tuned control characterise the HTK 1200N.
mounting, and four cable gland options for diesel components and measures info@panalytical.com
ensure compatibility on any site. The the content of total aromatics,
detector takes a range of accessories for polynuclear aromatics and biodiesel. Ultrasonic transducer for liquid
harsh or wet conditions and for Based on a stored number of calibration levels in corrosive atmospheres
remote sampling. samples, it predicts such important The Siemens Division Industry
salesusa@crowcon.com properties as Cetane number, Cetane Automation has added a PVDF
index or distillation properties like T85, (polyvinylidene fluoride) nose cone as
Separating process oils T90 and T95. an option to the non-contacting ST-H
from water Derived of information from the ultrasonic level transducer for liquids.
The Suparator technology from Aqueous spectrum, the new method calculates This new material type improves the
Recovery Resources effectively separates biodiesel content in diesel. Two areas in chemical compatibility of the ST-H
process oils and other liquids, along the spectrum are used for the transducer, offering more options for
with suspended contaminants from measurement: around 1745cm-1 for chemical storage and process vessel
water. The patented system, based on lower and 1170cm-1 for higher biodiesel applications. When paired with a
Bernoulli’s Principle of physics, enables content. FAME concentration is then Siemens ultrasonic controller, the ST-H
users to separate liquids differing in determined by calculating the spectrum transducer effectively measures the
specific gravity, thus making significant area rather than determining the height level of liquids in applications up to
savings in water consumption by of the ester peaks compared to the 10m (33ft) away in conditions from -40
allowing for the reuse of the water as baseline. The new method yields results to +73°C (-40 to 164°F). The transducer
well as other process fluids, such as with better accuracy than required by design includes both a 1in and 2in
separated oil. This saving of water also the biodiesel method EN 14078 and is integral process connection. This allows
improves uptime, extends the use of suitable for the determination of FAME easy mounting on varied vessels. When
detergents and significantly reduces the up to 40 wt%. A complete diesel installed using the 2in mounting
need to prepare water, thus saving measurement can be done in just three threads, the only wetted parts are PVDF,
on energy. minutes, making the IROX Diesel the providing excellent chemical immunity
Application of this principle achieves ideal instrument for fast and accurate in corrosive atmospheres. The ST-H
perfect separation of any two fluids with testing of diesel and biodiesel blends in transducer is impervious to dust,
a specific gravity differential. Unlike the laboratory or directly on-site. moisture, corrosion, vibration, flooding
conventional water separation devices, info.grabner-instruments@ametek.at and temperature extremes. The non-
it uses no moving parts or media to contacting design virtually eliminates
provide over 99% separation of polluting X-ray diffraction of the nuisance, danger and expense of
oils or liquid contaminants from water capillary samples cleaning, adjusting and repair associated
while it is still in the process tanks, thus Modern materials science demands with contacting devices.
saving a typical industrial user millions sophisticated tools to perform rob.niezen@siemens.com
of gallons of water each year. This liquid- investigations in defined environments
liquid separation allows for the reuse of and under controlled temperature Editor’s note
recovered contaminants, like oil, as well conditions. Non-ambient X-ray PTQ would like to bring to the attention
providing a means of reuse for it. Plus, diffraction (XRD) is established for a of its readership the recent acquisition
because separation is accomplished wide range of industrial and research by Shell Global Solutions International
dynamically, Suparator is able to remove applications. Now, a new capillary BV of 100% of the shares of Cansolv
dirt and other unwanted foreign objects extension expands the capabilities of Technologies Inc. Cansolv offers
from the suspended oil before they can this already powerful combination. The technology for the control of sulphur
settle into the water tank and necessitate novel accessory creates a two-in-one dioxide (SO2) and other contaminants
water and/or detergent changes. The reflection and transmission high- as well as a carbon dioxide (CO2) process
technology has also been already temperature XRD system. for greenhouse gas emissions capture,
deployed on an exploratory basis PANalytical’s PreFIX concept allows and has published an article pertaining
in petrochemical plant effluent seamless integration of the new to this technology in this issue,
pretreatment, crude washing and other Capillary Extension, transforming the beginning on p127, “SO2 scrubbing in
applications. HTK 1200N High-Temperature Oven refinery applications,” by Rick W
info@suparator.com Chamber into a high-end capillary Birnbaum.

www.eptq.com PTQ Q1 2009 143

Q1 2009 Ad Index.qxd 10/12/08 22:46 Page 1

ALPHABETICAL LIST OF ADVERTISERS

COMPANY PAGE COMPANY PAGE
NAME NUMBER NAME NUMBER
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BASF Catalyst 34 Onis International 102

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Compressor Controls Corporation 113 Rentech Boiler Systems IBC

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Consolidated Contractors Group 82 Samson 135

CRI Catalyst Company 109 Saudi Aramco 95

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Dupont Belco Clean Air Technologies 119 Shell Global Solutions 64

Emerson Process Management (Fisher) 101 Siemens - Sitrans 37

Euro Petroleum Consultants 43 SpectraSensors 130

ExxonMobil Research and Engineering Company 116 Spectro Analytical Instruments 126

FCC Client Study 58 Sulzer Chemtech 57

Flexitallic 85 ThyssenKrupp VDM 51

GE Oil & Gas 2-3 Tricat Catalyst Service 52

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W C Heraeus 86 UOP 38

Hoerbiger Kompressortechnik Holding 13 URS Washington Division 90

Honeywell Enraf 80 Vereinigte Füllkorper-Fabriken & Co 21

ITW 61 Weka 45

Johnson Matthey Catalysts 32 World Refining Association 136

KBC Advanced Technologies 4 Worley Parsons 105

KBR 11 www.eptq.com 48, 114

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Y OU CAN ACCESS INFORMATION AND CONTACT ADVERTISERS DIRECT AT

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144 P T Q Q1 2009 www.eptq.com

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