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catalysis
2021

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CATALYST
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 MAKE EVERY
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 catalysis Security of
ptq
feedstock supply
2021 Vol 13 No 2 3 Every little helps
www.digitalrefining.com
2008 Chris Cunningham

D
Editor 5 catalysis q&a
espite signs in 2007 of a slowdown in various sectors of the economy,
René G Gonzalez refiners remain a big play for prospective investors. It used to be
editor@petroleumtechnology.com
27 conventional
Tail gas hydrotreating
wisdom thatinhigher a highfuel
H2Sprices
gas plant
and a slowing economy
would curb demand and increase
Zhang Xiaogang, Wei Jinghui and Zhang Wenbin supply, but for the past seven years
Production Editor that has not proved to be the case. While the rate of increase in world oil demand
Sinopec
has declined since the surprising 4% surge in 2004, it nevertheless appears that
Rachel Zamorski
production@petroleumtechnology.com demand beyond 2008 will grow, along with prices. It is a safe bet that rapidly
increasing
33 oil consumption
Catalytic answer by toChina, Indiacracking
a steam and evenchallenge
the Middle East producers
themselves will continue. It is also safe to assume that refinery and petrochemical
Graphics Editor Marie-Clotilde Gouvenot and Yoeugourthen Hamlaoui
conversion unit capacity will need to expand.
Mohammed Samiuddin No massive Axens new sources of energy are expected to come on stream for the
graphics@petroleumtechnology.com
foreseeable future. The world will remain dependent on oil and gas for decades to
come39 even Refinery’s
though theperformanceupstream industry confirmsfaces increasing
catalyst challenges in the
testing
Editorial discovery and production of new sources. In fact, some well-placed industry
analysts think Tiago2008 Vilela,
may Nicolas
be the year Popoff
whereand Mark
there Moser
is no increase in crude supply at
PO Box 11283
Spring TX 77391, USA all from regions Avantiumoutside of OPEC. For this reason, we will continue to see significant
tel +1 281 374 8240 investment in refinery upgrades despite surging costs — security of feedstock
fax +1 281 257 0582 supply, albeit unconventional low-quality feedstock, takes precedence over the
45 Increased propylene from heavier residues
quality of feedstock supply.
FeedstockKuniaki
optionsManabe Taiyo Oil
such as biomass Company
(for biofuels production), Canadian tar sands
Advertising Sales Manager (for distillateCarel
production) and other types of unconventional crude sources require
Paul Mason Pouwels, Pao Sheng Wang and Tomochika Kotani
reactor technology that allows for the integration of these operations into existing
sales@petroleumtechnology.com Albemarle Catalysts
process configurations. The quality of these types of feedstock are one important
Advertising Sales reason why a wider array of catalysts has been introduced into the market. For
Bob Aldridge 51 asMore
example, refiners from cutthe barrel
deeper into the vacuum tower, the concentration of
sales@petroleumtechnology.com metals in the Sergio A Robledo and Perdesigned
VGO requires a properly Zeuthenguard bed system to protect active
catalysts in the hydrocracker. The characteristics of feedstock with low API gravity
Advertising Sales Office (eg, <10), high Haldor Topsoe
metals, nitrogen and other undesirable components is one of the
tel +44 870 90 303 90 main reasons why hydrotreaters and hydrocrackers are becoming larger — to
fax +44 870 90 246 90 accommodate not onlyprofit higherinvolumes of catalyst,
56 Increasing hydrocracking andbut also hydroprocessing
diesel a wider variety of
catalyst with specific formulations.
Publisher Keith Wilson, Louis Burns, Dean Parker and Padmini Lingaraju
Non-catalytic processes are also playing a significant role in the refiner’s ability
Nic Allen
publisher@petroleumtechnology.com
ExxonMobil
to process whatever unconventional crude sources become available. For example,
some refiners processing
Pieter Lusse,higher volumes of
René Severens andresid and atmospheric
Natasja tower bottoms
Berg-Schouten
Circulation have considered adding certain types of solvent-extraction processes in addition
Albemarle
Jacki Watts to overall improvements to crude unit (eg, vacuum tower revamps) and delayed
circulation@petroleumtechnology.com coker operations. Improvements in furnace technology, such as with olefin steam
cracker61operations,
Catalysthave switch solves
resulted NOx removal
in significant issues
increases in worldwide ethylene
Crambeth Allen Publishing Ltd capacity. Ken Wohlgeschaffen Chevron Products Company
Hopesay, Craven Arms SY7 8HD, UK However, any expansion of the value chain (eg, ethylene-to-propylene via
tel +44 870 90 600 20
dehydrogenation) Klavs Beldring Umicore in catalytic-based processes, as discussed in
requires investment
fax +44 870 90 600 40
the following articles authored by experts in the field of downstream process
ISSN 1362-363X technology. PTQ wishes to extend its gratitude to the authors who provided
editorial and responded to the Q&A published in this issue of PTQ Catalysis, as
well Cover
as to those respondents who addressed the online questions (www.eptq.com)
Petroleum Technology Quarterly (USPS
that Steam Cracker II at BASF Ludwigshafen, Germany
addressed the specifics of certain reactor and catalytic issues of importance to
Photo: BASF
0014-781) is published quarterly plus the industry.
annual Catalysis edition by Crambeth Allen
Publishing Ltd and is distributed in the USA
by SPP, 75 Aberdeen Rd, Emigsville, PA 17318. ©2021. The entire content of this publication is protected by copyright full details of which are available from the publishers. All rights
Periodicals postage paid at Emigsville PA. reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means – electronic,
Postmaster: send address changes to mechanical, photocopying, recording or otherwise – without the prior permission of the copyright owner.
Petroleum Technology Quarterly c/o PO 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 and its supplements the publisher cannot be held
Box 437, Emigsville, PA 17318-0437
responsible for any statements, opinions or views or for any inaccuracies.
Back numbers available from the Publisher
at $30 per copy inc postage. René G Gonzalez

ed cont copy 7.indd 1 25/02/2021 15:55

COLLABORATIVE. COMMITTED.
VALUED-ADDED PARTNER.
Our customers do important work and deserve a collaborative partner who is committed to
delivering value-added solutions.

When you partner with Albemarle, we bring extensive knowledge and deep application experience
to help you tackle your toughest challenges. Our innovative and diverse portfolio of refining
catalysts are designed by our technical experts to provide flexible, performance-based solutions
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catalysts solutions partner.

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 catalysis Security
Every littleof
helps
ptq
feedstock supply
Vol213 No 2
Vol 26 No
2021 2008

DT
Editor espite signs in 2007 of a slowdown in various sectors of the economy,
Editor René G Gonzalez
refiners remain a big play for prospective investors. It used to be
Chris Cunningham
editor@petroleumtechnology.com his 2021 issue of Catalysis features a Q&A section that breaks all records for
conventional wisdom that higher fuel prices and a slowing economy
editor@petroleumtechnology.com content. Warm thanks to our respondents for their insights, expertise, and
would curb demand and increase supply, but for the past seven years
news of developments. Indeed, special thanks to contributors affected by
Production
Production Editor Editor that has not proved to be the case. While the rate of increase in world oil demand
Rachel Zamorski
Rachel Storry has the recentsince
declined ‘polarthe storm’ that in4%
surprising particular
surge inhit Texas,
2004, who found the
it nevertheless time and
appears that
production@petroleumtechnology.com
production@petroleumtechnology.com demand beyond 2008 will grow, along with prices. It is a safe bet thattorapidly
opportunity to provide responses. The latest extreme weather event affect
the states
increasing oil sharing
consumption the Gulf bycoastline
China, India will require
and even some thetime
Middle for East
recovery, both
producers
Graphics personal and industrial.
themselves will continue. It is also safe to assume that refinery and petrochemical
Graphics Editor
Peter Harper Environmental
conversion unit capacity issueswillcomeneedto tothe fore in the replies to a question on the
expand.
Mohammed Samiuddin
graphics@petroleumtechnology.com
Nofeasibility
massive of new recovering
sources ofnon-precious
energy are expected metals from to come spentoncatalyst
stream (begin-
for the
graphics@petroleumtechnology.com ning onfuture.
foreseeable page 23). TheIs it economically
world will remain worthwhile
dependent on to oil
gleanandthe gaslikes of nickel
for decades to
Editorial
come andeven
cobalt, for instance,
though the upstream from refi nery waste?
industry facesOrincreasing
is it best to take the simple
challenges in the
tel +44 844 5888 773
Editorial
fax +44 844 5888 667 landfilland
discovery approach?
production of new sources. In fact, some well-placed industry
PO Box 11283 analystsWhatthinkis the
2008 value
maytobea the refiyear
ner of recovered
where there metals? As always
is no increase in an
in crude assess-
supply at
Spring
Business TX 77391,
Development USA
Director mentregions
all from of theoutside
industry’sof OPEC. economics, answersweare
For this reason, willfar from straightforward.
continue to see significant
tel +1 281 374 8240
Paul Mason Storing spent
investment in reficatalyst is an expense,
nery upgrades despite landfisurging llingcosts
even—more so. Furthermore,
security of feedstock
fax +1 281 257 0582
sales@petroleumtechnology.com simply
supply, burying
albeit the evidencelow-quality
unconventional could well feedstock,
have a detrimental impact onover
takes precedence a refithe
n-
er’s of
quality reputation
feedstockfor environmental care. Who can calculate the potential for lost
supply.
Advertising Sales Office
value in that
Feedstock options case? suchTheasvagaries
biomassof (for metals
biofuels trading might favour
production), Canadian recovery this
tar sands
telAdvertising
+44 844 5888Sales
771 Manager
(for week, but next week maybe not.
distillate production) and other types of unconventional crude sources require
fax +44 844Paul
5888Mason
662
reactor Sotechnology
what, in process that allowsterms, foristhe
theintegration of these The
route to recovery? operations
pages of intoPTQ existing
have
sales@petroleumtechnology.com
Managing Director process confi gurations. The quality of these types
from time to time highlighted a well established business based on pyromet-of feedstock are one important
Richard Advertising
Watts Sales reason why the
allurgy, a wider
process array of catalysts
of roasting spent has been introduced
catalyst to recover preciousinto the metals
market.such For
Bob Aldridge
richard.watts@emap.com example, as refiners cut deeper into the vacuum
as platinum. One of our Q&A correspondents, on the other hand, draws atten- tower, the concentration of
sales@petroleumtechnology.com metals in the VGO requires a properly designed guard
tion to the growing role of hydrometallurgy in metals recovery. In this case, bed system to protect active
Circulation catalysts in the hydrocracker. The characteristics of feedstock with low API gravity
lower-valued metals are leached from spent material. This is also an industrial
FranAdvertising
Havard Sales Office (eg, <10), high metals, nitrogen and other undesirable components is one of the
tel +44 870 90 303 90
circulation@petroleumtechnology.com process with a lengthy history. For example, a fair amount of the cobalt in cat-
main reasons why hydrotreaters and hydrocrackers are becoming larger — to
fax +44 870 90 246 90 alysts employed in desulphurisation originates in central Africa where linear
accommodate not only higher volumes of catalyst, but also a wider variety of
EMAP, 10th Floor, Southern House, heaps of mined ore are sprayed with concentrated sulphuric acid (which in
catalyst with specific formulations.
Publisher
Wellesley Grove, Croydon CR0 1XG turn is more processes
Non-catalytic likely than arenotalsoproduced
playing afrom signifithe output
cant role in of the
a refi nery’s
refi ner’s or gas
ability
Nic8695
tel +44 208 253 Allen plant’s sulphur recovery unit). The resulting liquor is processed before pass-
publisher@petroleumtechnology.com to process whatever unconventional crude sources become available. For example,
some ingrefi
toners
the electrowinning
processing higher plant where of
volumes cobalt
residmetal
and is recovered. tower bottoms
atmospheric
ISSN 1362-363X
Circulation Recovering metals from refi nery waste
have considered adding certain types of solvent-extraction processes is more likely than open-plan
in addition ore
Register to Jacki
receiveWatts
your regular copy of leaching to require the approval of health and
to overall improvements to crude unit (eg, vacuum tower revamps) and delayed safety inspectors. In a process
circulation@petroleumtechnology.com
PTQ at www.eptq.com/register cokerdevised by theImprovements
operations. Indian Institute in of Technology,
furnace spent catalyst
technology, such as with is first roasted
olefi n steamto
around
cracker 700°C, then
operations, haveleached
resultedwith acid before
in signifi a sequence
cant increases in of chemicalethylene
worldwide conver-
Crambeth Allen Publishing Ltd sions produces a suitable electrolyte for metal recovery. If there is demand, the
capacity.
Hopesay, Craven
PTQ (Petroleum Arms
Technology SY7(ISSN
Quarterly) 8HD, UK technology
However, anywillexpansion
emerge. of the value chain (eg, ethylene-to-propylene via
No: 1632-363X, USPS No: 014-781) is published
telplus
+44 870 90 600edition20
quarterly annual Catalysis by Crambeth Returning torequires
dehydrogenation) the value of recovered
investment metals, this
in catalytic-based page in
processes, past years
as discussed in
fax +44 Ltd870
and is 90 600 in40
the addressed the issue of rare by earth metals, theirfieldsources (just one, really),
Allen Publishing distributed the US
by SP/Asendia, 17B South Middlesex Avenue, following articles authored experts in the of downstream process
Monroe NJ 08831. Periodicals postage paid at New and theirPTQ
technology. prices inflating
wishes by multiple
to extend factors to
its gratitude of tenthe when
authors supplies became
who provided
Brunswick, ISSN 1362-363X
NJ. Postmaster: send address changes to
PTQ (Petroleum Technology Quarterly), 17B South restricted.
editorial Catalyst suppliers
and responded to the Q&A responded publishedin theinbestthiswaysissuethey could,
of PTQ including
Catalysis, as
Middlesex Avenue, Monroe NJ 08831. welldevelopment of non-rarewho
as to those respondents earthaddressed
material.the Is this
onlinea local crisis due
questions for a repeat
(www.eptq.com)
Back numbers available from the Publisher
at $30 per copy
Petroleum inc postage. Quarterly (USPS
Technology
thatperformance?
addressed theIfspecifi so, thecs of calculation
certain reactor in favour of metalsissues
and catalytic recovery is certainly
of importance to
0014-781) is published quarterly plus the more straightforward.
industry.
annual Catalysis edition by Crambeth Allen
Publishing Ltd and is distributed in the USA
by SPP, 75 Aberdeen Rd, Emigsville, PA 17318.
Periodicals postage paid at Emigsville PA.
Postmaster: send address changes to CHRIS CUNNINGHAM
Petroleum Technology Quarterly c/o PO
Box 437, Emigsville, PA 17318-0437
Back numbers available from the Publisher
at $30 per copy inc postage. René G Gonzalez
Catalysis 2021 3

ed cont copy 7.indd 2 25/02/2021 17:18

 Process Notes

Vacuum tower cutpoint delivers profits

Cutpoint Concerns poorly designed heaters may experience coking with

COT below 700°F (370°C).
Crude unit vacuum tower performance is often critical
to a refiner’s bottom line. The vacuum tower bottoms Flash zone pressure is set by vacuum system
stream is valued far below the gas oil cuts, so most performance and column pressure drop. Lower flash
refineries look to minimize it. Many vacuum columns zone pressure increases cutpoint until the tower shell
are also designed or revamped to produce a diesel cut, C-factor limit is reached, at which point the packed
recovering diesel slipped from the atmospheric column beds begin to flood. Vacuum producing systems are
that would otherwise be downgraded to VGO product. mysterious to many in the industry, so a large number
of refiners unnecessarily accept poor vacuum system
Good vacuum column performance can maximize the
performance. With technical understanding and a good
profitability of downstream units by removing distillate
field survey, the root causes of high tower operating
hydrotreater feed (diesel) from FCCU or hydrocracker
pressure can be identified and remedied.
feed (VGO) and removing VGO from coker feed (resid).
In columns with stripping trays, stripping steam rate
One important measure of vacuum column
and tray performance are important. Stripping steam
performance is VGO/resid cutpoint. The cutpoint is the
rate is limited by vacuum column diameter (C-factor)
temperature on the crude TBP curve that corresponds
and vacuum system capacity. Any steam injected into
to the vacuum tower resid yield.
the bottom of the tower will act as load to the vacuum
system, so vacuum system size, tower operating
Vacuum column cutpoint depends on three variables:
pressure, and stripping steam rate must be optimized
1. Flash zone temperature
together. Depending on the design, a stripping section
2. Flash zone pressure
with 6 stripping trays can provide between zero and
3. Stripping section performance (if present)
two theoretical stages of fractionation, which can drive
Flash zone temperature is driven by vacuum heater coil a big improvement in VGO yield.
outlet temperature (COT). Increasing COT increases
Although the variables for maximizing vacuum tower
cutpoint. Vacuum heater outlet temperature is typically
cutpoint are simple, manipulating them to maximize
maximized against firing or coking limits. When
cutpoint without sacrificing unit reliability is not.
processing relatively stable crudes, vacuum heaters
Contact Process Consulting Services, Inc. to learn how
with better designs and optimized coil steam can avoid
to maximize the performance of your vacuum unit.
coking even at very high COT (800°F+, 425°C), but

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Suite 130 info@revamps.com
Houston, TX 77005, USA www.revamps.com

pcs cutpoint.indd 1 16/09/2020 12:05

 catalysis q&a

Q What are the symptoms of silica poisoning of a exotherm moves through the catalyst bed as silicon poi-
hydrotreating catalyst? How is it best avoided? soning occurs provided there are enough thermocou-
ples and/or there are multiple beds in the unit. This is
A Ashok Monteiro, Technical Service Manager, Advanced a useful way to track the progression of silicon through
Refining Technologies LLC (ART), Ashok.Monteiro@Grace.com the reactor.
In order to understand the impact and options to mit- Besides the silicon encountered in naphtha from
igate silica poisoning, it is important to understand cokers, silicon can also be found in synthetic crudes
the mechanism of silica poisoning. The silica does not because the process of making synthetic crude often
poison the active metal sites directly, but rather restricts involves a coking step. Many crude suppliers have also
the pore structure, and eventually blocks access to the used additives containing silicon in drilling processes,
active sites. This phenomenon is referred to as pore and pipeline companies are using silicon containing
mouth plugging and is associated with a characteristic additives injected into the crudes for both flow enhanc-
deactivation pattern. ing performance and foaming issues. As a result, even
The main source of silica is from delayed coker refiners who do n0t have coking capabilities may run
operation which uses an anti-foam agent based on into Si contamination issues.
polydimethylsiloxane to suppress foaming in the coker Refinery economics often dictate that opportunity
drums. Lower molecular weight silica gels are formed crudes be processed to maximise profitability. Given
as the siloxane complex breaks down in the coking pro- this limitation, many refiners opt to have a coker unit
cess. Catalysts with a high alumina surface area are typ- in their configuration which makes it hard to avoid
ically used to trap silicon efficiently from coker naphtha silica poisoning. Better monitoring and optimisation of
containing modified silica gels. As the silicon content in the coker unit is one way to reduce the impact of silica
the catalyst increases, the surface area is progressively poisoning. Another option is to use high surface area
used up which affects the hydrotreating activity of the catalyst that is effective at trapping Si to help mitigate
catalyst. The impact of silica poisoning does not become some of the poisoning issues.
evident in the initial stages as there is a period of mod-
est activity loss followed by more rapid deactivation as A Per Zeuthen, Senior Director, Europe, Haldor Topsoe,
the available surface area is plugged with silica. As a pz@topsoe.com
result, silicon contamination is a major concern in units Silicon species are typically found in coker-derived
treating coker naphtha. In these units, the rate of silicon products, and they act as poisons to the hydrotreating
deposition on the catalyst is usually what determines catalysts. The origin of silica can typically be traced
run length rather than coke deactivation. In extreme back to the silicone oil added to the heavy residue feed
cases of contamination, cycle lengths can be as short as to the coker. However, silicone oil is added in other
three to six months. streams as well. Silicone oil will crack or decompose to
A prominent aspect of catalyst deactivation by sil- form modified silica gels and fragments when heated
ica contamination is the relative rates of deactivation to high temperatures. These gels and fragments are
for HDS and HDN. The loss in HDN activity tends mostly distilled in the naphtha range and are therefore
to be more rapid than for HDS activity even though carried to the downstream hydrotreaters together with
pore mouth plugging should affect them equally. This the coker naphtha. Silicon poisoning of the catalyst in
is a reflection of the different reaction mechanisms for the hydrotreaters reduces the overall catalyst activity,
HDS and HDN. This phenomenon can be useful to the however in particular the silicon poisoning impacts and
refiner because nitrogen breakthrough typically pre- reduces the HDN activity. As mentioned, the silicon
cedes silica breakthrough. It is much easier to analyse poisoning impacts all catalyst functionalities, such as
for nitrogen in the product than it is to analyse for sil- HDS, HDN, as well as saturation activities, but in par-
icon. This gives the refiner a way to anticipate silicon ticular the HDN activity. Reduction in HDN activity is
breakthrough and prevent contamination of the down- therefore the first sign of catalyst deactivation due to
stream noble metal reforming catalyst. silica poisoning.
It is critical to monitor the operation of the unit and If you cannot avoid silicon in the feed to the hydro-
optimise the bed operating temperature as the silicon treating catalysts, then the best way to delay the nega-
pickup is a temperature dependent catalytic reaction. At tive effects is to use catalysts with the highest possible
start of run (SOR), most of the reaction occurs near the silicon capacity, as well as to include high-silicon capac-
top of the catalyst bed. Over 50% of the delta tempera- ity products as part of the catalyst grading in the top of
ture occurs between the top and middle of the catalyst the unit to protect the downstream catalysts the most.
bed. As the cycle progresses, and the catalyst at the top There are significant differences in silicon capacities
of the bed is poisoned, the exotherm shifts to lower in comparing the different available commercial hydro-
the catalyst bed. It is often possible to monitor how the treating catalysts. Haldor Topsoe has a very strong and

www.digitalrefining.com Catalysis 2021 5

Q&A copy 27 (original).indd 1 23/02/2021 16:28

 well-recognised series of catalysts, our TK-4xx catalyst hydrodenitrogenation function, and a relatively steeper
series, with very high silicon capacities. pressure differential rise rate. At half of their repre-
sented silicon capacity, the activity of high Si capacity
A Guillaume Vincent, Business Segment Manager HPC, naphtha hydrotreating catalysts will be approximately
Porocel, gvincent@porocel.com half vs fresh, tracked indirectly via bed-by-bed exo-
Silicon is the most common contaminant for hydrotreat- therm reduction rates.
ing units. Silicon contamination is a major concern for Silica poisoning is best managed with a comprehensive
coker naphtha, but small quantities can be found in the strategy: 1) managing foaming in the delayed coking
diesel and kerosene fractions. The use of anti-foaming process according to industry best practices; 2) using
agents (mainly polydimethylsiloxane, PDMS) in delayed only the most thermally stable polysiloxanes for the low-
coker operations can lead to about 80% of silicon ending est polysiloxane dosing; 3) regularly monitoring elemen-
up in the coker naphtha fractions. Typically, PDMS is tal silicon concentrations in the hydrotreating feedstock
thermally decomposed as cyclic siloxanes, which induce components and product streams; 4) carefully specifying
pore mouth plugging and deactivation of the main cata- silica adsorbents and hydrotreating catalysts appropriate
lyst bed. Up to 6°C of activity loss for each 1.0 wt% of Si for the expected siloxane species; and 5) operating the
on the hydrotreating catalyst is possible due to decreased silica adsorbents and hydrotreating catalysts in a tem-
accessibility of active sites leading to higher weighted perature range known to be especially effective for silica
average bed temperature (WABT) to achieve the desired adsorption, from start-of-cycle. Cycle-by-cycle vacuum
specifications in the product. This deactivation phenom- unloading can provide a record of catalyst capacities
enon will result in shorter cycle length, underperfor- and inform decisions related to catalyst reuse. Regular
mance of the unit, and shutdown of the unit for catalyst application of sectioned catalyst baskets will likewise
change-out. help to inform future catalyst selections. The strategy
In order to maximise the HDS/HDN reactor perfor- may even include dedicated lead/lag or swing guard
mance, Legacy Porocel, now part of Evonik, has specially beds upstream of the hydrotreater and/or mid-cycle
designed CatGuard Si21 as a silicon trap to: reactor skims. Phosphorus may likewise be included
• Gently saturate the olefins and mitigate the delta pres- in the management strategy, as phospholipid and/or
sure build-up phosphatide anti-wear/lubricant products are also com-
• Trap silicon due to its high surface area (silicon capac- monly injected to improve crude oil recovery rates. Such
ity ≥ 20 wt%) compounds will thermally decompose and can lead to
• Maximise volumetric retention hydrotreating catalyst poisoning downstream, and these
• Minimise diffusional limitations due to its optimised are managed in a similar manner to siloxanes.
pore size structure
CatGuard Si21 silicon trap is a key part of Legacy A Chad A. Perrott, Business Advisor, Albemarle, chad.perrott@
Porocel’s hydroprocessing product line. Legacy Porocel’s albemarle.com
technology portfolio enables refiners to meet their prod- The first indications of a silicon (Si) poisoning event
uct quality and cycle length targets in hydroprocessing within a hydrotreating catalyst system are usually
applications for a fraction of the cost of conventional detected in the feed, which when sampled shows
catalysts. CatGuard Si21, as a part of the top bed grading increases in the average Si levels exceeding the design of
supply, will allow refiners to: the system.
• Maximise unit performance The most common kinetic symptoms of Si poisoning
• Protect against poisoning are a general loss of hydrogenation activity (including
• Increase life cycle hydrodenitrogenation, HDN) and reduced olefin satura-
tion activity. For heavier feed units with more sterically
A Steven Zink, Principal R&D Engineer/Scientist, Honeywell hindered heteroatoms, the hydrogenation losses can
UOP, Steven.Zink@honeywell.com also affect the hydrodesulphurisation (HDS) reactions.
Silica poisoning of hydrotreating catalysts is ordinarily Eventually, Si slippage to the product may become evi-
incurred by the processing of streams that are laced with dent. All the aforementioned can result in reduced cycle
siloxanes, derived from the thermal decomposition of length.
polysiloxanes. Polysiloxanes are routinely injected to The level of Si poisoning should be determined after
improve crude oil recovery rates and to moderate foam- the cycle is completed and before regeneration to avoid
ing in the delayed coking process. Thermal cracking of formation of mixed silicon-molybdenum oxidic phases
polysiloxanes renders the majority into the naphtha, during regeneration. This is important if catalyst regen-
then diesel, then VGO boiling ranges. The siloxanes are eration is considered since mixed silicon-molybdenum
catalytically hydrotreated, leading to silicon tying up oxidic phases cannot be sulphided and will result in
the hydrotreating catalyst support’s surface hydroxyls, lower than expected activity when reloaded.
accumulating over time, and eventually obstructing Even if the catalyst is not to be regenerated, know-
adsorption at the active metal sulphides. The most ing the Si poison level after unloading is important to
effective catalysts have a combination of high surface enable the planning of future cycles. The knowledge
area and porosity that is compatible with the size of the from these samples can help optimise the Si traps for
siloxane species. Silica poisoning manifests itself as a future loads. The benefit of optimisation is that future
relatively steeper deactivation rate, particularly of the cycles can be extended and/or opex can be reduced

6 Catalysis 2021 www.digitalrefining.com

Q&A copy 27 (original).indd 2 23/02/2021 16:28

 SPECIALIZED CATALYSTS
JOINTLY DEVELOPED SOLUTIONS FOR CLEANER FUELS
AND MAXIMUM PERFORMANCE

Together with Advanced Refining Technologies LLC, CLG offers the most complete portfolio of
hydroprocessing solutions in the industry. We offer more experience than any other licensor providing leading
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to keep pace with changing market dynamics, start by visiting www.chevronlummus.com.

clg.indd 1 23/02/2021 15:33

 when spent catalyst is considered in the refinery. In cases where the
for regeneration. presence of silicon in the feedstock
X-ray diffraction (XRF) is used cannot be avoided, the next best
for simple quantitative analysis. solution is to use a suitably designed
Scanning electron microscopy guard bed on top of the main hydro-
with energy dispersive X-ray anal- treating catalysts. The silicon trap in
ysis (SEM-EDX) is a quantitative the guard bed will capture a large
method with a qualitative aspect part of the silicon, and thereby pro-
(see Figure 1). Both methods are use- tect the main (high activity) hydro-
ful to determine the Si poisoning on treating catalyst from deactivation.
spent catalyst. Figure 1 SEM-EDX of hydrotreating catalyst Most catalyst companies have sili-
There are multiple steps to avoid con traps in their portfolio and they
silicon poisoning in hydrotreating catalyst. These include can supply the silicon trap as part of the full load. A cata-
proper planning and execution, monitoring the running lyst supplier will guarantee a silicon pickup of the silicon
unit, and analysing spent catalyst to inform the next trap and a cycle length of the unit in case their technical
planning cycle. offer is accepted. In case you want to design your own
During planning, it is important to communicate your guard bed, you can test several trap materials from dif-
typical feed contaminant levels with catalyst vendors. ferent suppliers in a basket in the hydrotreater and inves-
This critical information, in turn, provides vendors an tigate at the end of a cycle which trap shows the highest
opportunity to enhance metals pickup capability and removal on a weight or volume basis.
ensure management of Si poisoning. Technology like Some companies offer guard materials at reduced
Albemarle’s STAX enables refiners to meet increasingly prices. Obviously, if you design your own guard bed,
challenging feeds and processing goals in this way. Then you do not get a guarantee on the complete fill or a con-
during turnaround execution, it is crucial to load the cat- ditional guarantee based on silicon slip to main catalyst.
alysts as designed, and then maximise catalyst activation. After a first cycle with silicon in the feed it is important
When the unit is running, regular monitoring of con- to check the silicon on the spent catalyst to be regener-
taminants in the feed can help identify unexpected ated as silicon will cause deactivation upon regeneration.
changes that may harm the catalyst. This data is import- As a rule of thumb, a 1 wt% Si on regenerated catalyst
ant for determining errant sources of Si, including over- will cause a 20% RVA loss on a conventional type 1
use of anti-foaming agents such as organo-polysiloxanes hydrotreating catalyst. Reactivation of a type 2 hydro-
from delayed coker units, identifying off-spec import treating catalyst is only possible if the silicon level is
barges or, more recently, changes in tight oil qualities. low (typically below 1 wt%), as specified by the original
Conducting normalised catalyst activity reviews supplier.
during operation can assist in identifying unexpected
catalyst deactivation. Maintaining a sum of the total Si A Tom Ventham, Sales & Technical, Europe and Africa, Unicat
imported to the unit can help enable rationalisation of B. V. / G. W. Aru, LLC, tom.ventham@gwaru.com
opportunity feeds to the refinery while balancing Si poi- Silica is a known issue for hydrotreating catalyst. A
soning effects on the cycle. common source of silica are coking operations that
Finally, sampling spent catalyst at various catalyst lay- use certain anti-foaming chemicals.1 In applications
ers and analysing via SEM-EDX or XRF for metals con- not fed by delayed cokers, silicon can still be found in
tamination can help identify necessary adjustments in the hydrotreater. This can derive from processing of
metals traps for subsequent loadings. synthetic crudes, which often employ coking steps in
their production, or use of regular crudes from new
A Carl van der Grift, Director, Catalyst Intelligence, or existing sources where drilling and flow improve-
vandergrift@catalyst-intelligence.com ment chemicals are injected into wells and pipelines to
Silicon contamination of hydrotreating catalysts is assist recovery. Once silicon enters the hydrotreater, it
caused by silicon compounds entering the hydrotreater can bind with the alumina surface and an activity loss
with the feed. The silicones in the feed may originate will be observed. A common rule of thumb is a 3-6°C
from drilling fluids and flow improvers used in the loss in temperature for every 1 wt% Si deposited on the
upstream, or from antifoaming agents used in the refin- catalyst. This activity loss cannot be recovered through
ery. A third source of silicon in the hydrotreater may be catalyst regeneration. When Si reaches 15-20 wt% on
clay, usually found in oil sands. High silicon levels will catalyst, only about 50-60% catalyst activity remains.
reduce the cycle length due to catalyst deactivation and/ Hydrotreating catalyst can be protected by installing
or pressure drop build-up, or both. Low silicon levels a highly effective guard material at the reactor inlet to
may not noticeably affect the cycle length of a fresh cat- trap silicon and prevent it entering the catalyst bed.
alyst in a first cycle, but accumulated silicon levels on a Unicat’s Active Filtration System-Silica Trap (AFS-ST)
spent catalyst may render it unsuitable for regeneration/ removes silicon and many other poisons found in pro-
reactivation. cess streams. As a specialised solution to remove silica,
Silicon deactivation is best avoided by limiting silicones grading systems using correctly sized AFS disks can be
in the feedstock. This can be done by feedstock selection implemented to help protect against poisoning issues.
and by being careful with the use of anti-foaming agents Using an efficient AFS-ST system allows the required

8 Catalysis 2021 www.digitalrefining.com

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 Best of Both Worlds

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cracking from a novel single particle
Thanks to our world-class R&D, manufacturing, and
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sacrificing the impressive coke selectivity, attrition resistance,
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grace.indd 1 23/02/2021 15:37

 grading outage to be minimised to maximise
the amount of catalyst that can be loaded into 100
the reactor.
An alternative approach is also available,
which is a skid mounted system containing

RSH/S, %
pre-loaded AFS baskets to condition the feed
upstream of process units. The advantages of
such a system include the flexibility to replace
spent grading baskets while the downstream w/Axens polishing RX conventional HDS

reactor remains online, avoiding costly down- 0

0 10 20 30 40 50
time. Another major advantage is the ability Product S, wppm
to increase catalyst volume by moving guard
material out of the main reactor. Figure 2 RSH contribution to total product sulphur for various specs
The benefits of using the AFS advanced
grading solution means run lengths can be increased, desulphurised naphtha, bypassing the HDS section and
catalyst life can be maximised, shutdowns and change- thereby preserving all the valuable light olefins.
outs can be delayed, and opportunity feeds can be The formation of mercaptans in the HDS section
explored whilst mitigating the dangers of catalyst through the addition of H2S to olefins is a critical matter
poisoning. when targeting ultra-low sulphur FCC gasoline (see
Figure 2). Basically, each ppm of mercaptan that is formed
inside the unit requires that an additional ppm of sulphur
Q Is there a route for post-treating gasoline with minimal from the feed be removed, which can dramatically impact
octane loss? octane retention since the octane loss increases exponen-
tially with the HDS rate. Axens offers several solutions,
A Olivier BOISIER, Technology Team Manager, Catalysts & both catalytic and schematic, to tackle this problem.
Adsorbents Global Business Unit, olivier.boisier@axens.net; On the road to high octane, one should also lean on the
Boris HESSE, Technologist, Catalysts & Adsorbents Global operation of the FCC as it can have big consequences for
Business Unit, boris.hesse@axens.net both the absolute octane value of the FCC gasoline and
For the post-treatment of FCC gasoline, fixed-bed HDT is octane retention in the post-treating unit. Higher FCC
by far the most trusted solution because of its low capex, severity for instance generally makes for a more aro-
its ease of operation, and its flexibility. This technology matic gasoline, which directionally has a higher octane
also allows for excellent octane retention provided there value (see Table 1). The olefins distribution is modified as
is combined use of smart schemes and highly specific well which has an impact on octane preservation in the
catalysts capable of very high HDS rates with mini- post-treating unit.
mum olefins saturation. Axens offers both as part of the The challenge for catalyst manufacturers is to provide
Prime-G+ trademark. catalytic solutions addressing high octane retention
A smart scheme should take advantage of the particu- along with high activity/contaminants tolerance as
larities of the FCC gasoline, the most striking being that those parameters generally go in opposite directions.
olefins are more concentrated in the light fraction of the High activity/contaminants tolerance is key to long
gasoline while sulphur is more concentrated in the heavy cycle lengths matching the FCC turnaround schedule
fraction (see Figure 1). The combination of the Prime-G+ and to important energy savings. With HR 845 for the
SHU reactor with the Prime-G+ splitter capitalises on SHU and the duo HR 806/HR 841 for the HDS boasting
this and allows for the production of an olefins-rich, more than 1000 cumulated references, Axens has created
benchmark catalysts for FCC gasoline post-treatment.
Capitalising on the feedback from nearly 200 running
Benzothiophenes units and relying on extensive R&D work conducted
Thiophenes S
jointly with IFPEN, Axens is now bringing to the market
S C2-Th C3-Th a full range of new Prime-G+ catalysts: HR 855 for higher
S
CH3
SHU activity, HR 856 for higher HDS selectivity and HR
Sulphides Sulphur
866 for higher HDS activity.
C1SC1 C1SC2 C2SC2 Olefins

Prime-G+ product quality as a function of FCC severity

Mercaptans
RSH, R = C1 to C5 Prime-G+ Average FCC High FCC
product quality conversion conversion
Gasoline flow rate, BPSD Base Base - 18%
Total sulphur, wppm 10 10
Olefins, vol% Base Base - 5%
Pl- 50- 70- 90- 110- 130- 150- 170- 190+ Aromatics, vol% Base Base + 25%
50 70 90 110 130 150 170 190
RON, # Base Base + 2.4
Cuts, ˚C

Figure 1 Olefins and sulphur distributions in FCC gasoline Table 1

10 Catalysis 2021 www.digitalrefining.com

Q&A copy 27 (original).indd 4 24/02/2021 19:16

 RETHINK
EVERYTHING
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The key to unlocking sustainable
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honeywell.indd 1 23/02/2021 16:05

 performance can be done quickly, with no cap-
ital investment, and with the potential to gen-
5
erate a significant increase in profitability.
Octane savings, MM$/y

A Claus Brostrøm Nielsen, Senior Solution

Specialist, Haldor Topsoe, clbn@topsoe.com
It is important to understand the molecular
composition of FCC naphtha before looking
1 bbl of RON = $1 1 bbl of RON = $0.5 at desulphurisation of cracked naphtha and
0 octane loss. If we look at boiling points of the
0 500 1000 1500
sulphur species, like mercaptans, thiophenes,
Prime-G+ SHU feed sulphur, wppm
and their derivatives, we can classify cracked
naphtha into two broad ranges: light cracked
Figure 3 Typical savings when loading HR 856 in place of HR 806 in a 20 000 naphtha (LCN) and heavy cracked naphtha
BPD Prime-G+ producing at Euro 5 (HCN). For better differentiation, it can be said
that fraction boiling above 80–85°C (176–185°F)
These new catalysts will help refiners take on new can be considered as HCN. Most of the sulphur in the
challenges and enhance further their profitability, allow- LCN fraction is mercaptans. The refractive sulphur spe-
ing them for instance to process more refractory/more cies are distributed in the HCN fraction.
contaminated feeds from both FCC and other sources The LCN fraction contains a large part of the total
(co-processing of coker naphtha, pyrolysis gasoline, and amount of olefins present in the FCC naphtha. Olefins
so on) and to reduce significantly both octane losses (see with carbon number 4, 5, and 6 will be present in the
Figure 3) and hydrogen consumption. LCN fraction, and olefins with higher carbon numbers
will be present in the HCN fraction. This is important to
A Colin Baillie, Segment Manager, Environmental know when going into design strategy for a post-treat-
Additives, W. R. Grace & Co, Colin.Baillie@Grace.com; George ment process specific for FCC naphtha. The main chal-
Hoekstra, President, Hoekstra Trading LLC, george.hoekstra@ lenge in FCC gasoline post-treatment is to selectively
hoekstratrading.com remove sulphur molecules while avoiding saturation of
One way to minimise octane loss in post-treated gaso- olefins, which are a major contributor to octane number
line is through adjusting the FCC process to optimise of gasoline. Saturated olefins have significantly lower
the properties of FCC gasoline, prior to the subsequent octane than the corresponding unsaturated molecules.
post-treatment. When increasing the sulphur removal, the olefin satura-
FCC gasoline typically consists of >300 different mol- tion and corresponding octane loss increase almost expo-
ecules, composed of paraffinic, olefinic, and aromatic nentially the closer you get to 100% HDS conversion.
structures. Portions of these molecules subsequently Typically, post-treatment of FCC naphtha consists of
undergo further hydrogenation reactions when post- a two-step process: selective hydrogenation of diolefins
treated, which leads to octane loss. The level of octane followed by a hydrodesulphurisation (HDS) step to
loss is strongly impacted by the specific olefins that are convert the sulphur species. Selective hydrogenation is
being saturated, for example saturation of linear olefins, undertaken at a low temperature compared to down-
branched olefins, and cyclic olefins will lead to different stream hydrodesulphurisation. Selective hydrogenation
levels of octane loss, as will the carbon number of the of cracked feed also transforms the light sulphur species
olefins. This is because these olefinic species have differ- into heavier sulphur-bearing molecules. With the trans-
ent octane values, as do the resulting paraffins that are formation of lighter sulphur species like mercaptans
formed upon post-treatment. The sulphur content of the into heavier sulphide molecules, an almost sulphur-free
FCC gasoline and type of sulphur species (mercaptans, LCN fraction can be obtained. These heavier sulphide
thiophenes, benzothiophenes) is also important, as it molecules will now end up in the HCN fraction. A typ-
impacts the post-treatment severity (and therefore octane ical layout of a post-treatment unit consists of a selective
loss) that is required to achieve a target sulphur level. hydrogenation unit, a splitter column to separate LCN
W. R. Grace & Co. and Hoekstra Trading LLC have and HCN, and then a hydrodesulphurisation unit (HDS).
worked together to provide unique insight into how The separation of LCN from HCN in the splitter, which
the FCC process can be optimised to reduce octane loss follows the SHU section, ensures that we end up with
of post-treated gasoline. Detailed hydrocarbon analysis LCN, which is sulphur-free, and HCN that needs to be
and sulphur speciation of FCC gasoline and the corre- hydrodesulphurised. The high octane of the LCN stream
sponding post-treated gasoline combined with Hoekstra can therefore be retained, since no further hydrodesul-
Trading’s software allow the analysis of individual reac- phurisation is required. The HCN fraction is sent to the
tions occurring upon post-treatment, and ultimately the HDS section.
octane impact of those reactions. Tailored FCC catalyst In the HDS section of the unit, hydrodesulphurisation
and gasoline sulphur reduction technology can then be of the HCN fraction takes place to meet the required
employed to optimise FCC gasoline properties for mini- sulphur specifications. Hydrotreatment catalysts
mum octane loss of post-treated gasoline. Such analysis with optimised activity and selectivity, which enable
has revealed that improving gasoline octane/sulphur removal of sulphur to ultra-low levels while retain-

12 Catalysis 2021 www.digitalrefining.com

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 A Better Perspective
on Hydroprocessing Solutions

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art.indd 1 23/02/2021 15:34

 ing high octane numbers, are the keys to a successful sulphur while minimising olefins saturation is required.
FCC gasoline post-treatment. Haldor Topsoe’s series Notably, by separating LCN from FCC naphtha, the
of HyOctane catalysts is specifically developed for all concentration of sulphur in the heavier fractions (ICN/
steps in the FCC gasoline post-treatment applications HCN) increases compared to the full range naphtha
and meets the requirements for optimised activity and itself, which makes it more challenging to treat.
selectivity which enable a profitable production of High activity RT catalysts, such as those manufac-
high-quality gasoline with minimum octane loss. The tured by Albemarle and developed for ExxonMobil
catalysts are designed with high selectivity, which min- SCANfining, have demonstrated high selectivity (high
imises mono-olefin hydrogenation even at ultra-low octane retention) in ULSG units processing high sul-
sulphur levels down to 10 wtppm. This ensures that a phur feeds ranging from ICN to HCN blends when Tier
high octane number is maintained in the final gasoline III product sulphur level is required. In addition, refin-
product. eries without fractionation capabilities that need to pro-
The Haldor Topsoe licensed HOT process (HyOctane cess full range FCC naphtha have also benefitted from
Technology) is developed to provide even better octane the market-leading high selectivity of RT catalysts.
retention than today’s available technologies. The HOT On the process side, high improvements have been
process is a combination of unit layout, process condi- obtained in lowering octane losses by applying pro-
tions, and the HyOctane catalysts, and when combined ficient post-treatment hydrotreating processes such
together it can obtain an ultra-low sulphur gasoline as SCANfining II (second generation SCANfining).
product with significantly higher octane value than Commercial experience demonstrates that at 10 wppm
typically seen from other FCC gasoline post-treatment product sulphur, SCANfining II saturates about half of
units. the olefin content compared to the original SCANfining
The route to FCC gasoline post-treatment with mini- process.
mal octane loss goes through the correct unit layout and The RT catalysts have also shown commercial success
selection of the optimum catalysts. in other post-treatment gasoline hydrotreating processes,
such as Axens’ Prime-G+.
A José A. Toledo, Technical Service Engineer, Albemarle,
joseantonio.toledo@albemarle.com A Steven Zink, Principal R&D Engineer/Scientist, Honeywell
FCC naphtha is the most common gasoline pool blend UOP, Steven.Zink@honeywell.com
component, accounting for 30-50% of the overall gaso- Assuming FCC pre-treat capacity installation is not an
line blend, and is the biggest contributor with respect to option, sufficiently low octane deltas on post-treatment
sulphur. of FCC gasoline can be achieved via sequential applica-
With gasoline regulations focusing on product sul- tion of several key molecular management operations.
phur levels, post-treating FCC naphtha for reduced Light mercaptan sulphur is catalytically sweetened out
sulphur also impacts octane quality. However, because of the light-cut, highest octane olefin fraction, which is
many refiners lack FCC pretreatment capacity, cat naph- recovered as a distillate product in a gasoline fraction-
tha post-treatment remains a commonly applied solu- ator, with a recovery rate that is subject to the gasoline
tion. In any case, the key is to avoid large octane losses pool sulphur specification. The hydrotreating catalyst
that occur due to saturation of olefins during conven- processing the mid-cut should perform with a very
tional hydrodesulphurisation of full range cat naphtha. high ratio of desulphurisation rate vs olefin hydrogena-
Other processing options are available depending on tion rate, in one or two hydrodesulphurisation stages,
refinery choice but handling the different cat naphtha depending on the feed sulphur content and the maxi-
fractions (LCN, low boiling and ICN/HCN, intermedi- mum tolerable octane loss. At 10 ppm or less sulphur
ate/high boiling) separately is one of the most common specification (US Tier 3), this fraction will require pol-
approaches. It is widely known that olefin and sulphur ishing, due to olefin recombination with the hydrogen
content distribution in full range FCC naphtha moves sulphide produced in situ. Catalytic polishing of the
in opposite directions: most of the olefins, which are deeply desulphurised mid-cut, carried out at relatively
desired high octane contributors to the gasoline pool, higher temperatures where recombination is less ther-
are found in the lighter portion (LCN), while the major- modynamically favourable, should be leveraged as
ity of sulphur is concentrated in the intermediate and much as possible to retain more olefins. The hydrogen
high boiling range (ICN/HCN) fractions. partial pressure should be kept only just high enough to
By separating the lighter boiling range naphtha achieve the desired extent of desulphurisation, to limit
(LCN), a fraction is created wherein most of the sulphur octane loss by olefin hydrogenation.
compounds consist of light, low boiling point mercap- To limit the loss of olefins to recombination, the
tans and sulphides. These species are present in LCN in hydrogen sulphide partial pressure should be kept as
low concentration and are easy to desulphurise. Often, low as possible via application of a well-maintained
applying just sweetening processes is sufficient and amine scrubber to the recycle gas. The heavy gasoline
allows for the preservation of olefins compounds and fraction contains the lowest concentration of olefins
high octane. For deep removal of the refractory and (more aromatic than olefinic) and the highest sulphur
more concentrated sulphur compounds (thiophenes) concentration. Such sulphur is also the slowest to
in heavier fractions of the FCC naphtha (ICN/HCN), a convert, relative to the light-cut and mid-cut sulphur.
highly selective HDS that can specifically tackle difficult Considering that the few olefins in the heavy fraction

14 Catalysis 2021 www.digitalrefining.com

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 New ultra-high activity TK-6001 HySwell™ catalyst for
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haldor.indd 1 23/02/2021 15:31

 contribute the least to gasoline octane, the heavy frac- Q What are the benefits of bulk metal catalyst in
tion is best routed to a conventional naphtha hydro- hydrotreating?
treater, to enable greater production of high-octane
reformate gasoline. A Bi-Zeng Zhan, Hydrocracking R&D Manager, Advanced
Refining Technologies LLC (ART) bize@chevron.com;Theo Maesen,
A George Hoekstra, President, Hoekstra Trading LLC, george. Director R&D, Chevron Lummus Global, TMaesen@chevron.com
hoekstra@hoekstratrading.com Self-supported catalysts, sometimes branded as ‘bulk
Octane loss can be optimised with a good selection of catalysts’, pack high hydrogenation activity into a small
feed properties, splitter cut points, HDS reactor condi- reactor volume. The superior hydrogenation activity of
tions, HDS catalysts, FCC catalyst technology, and capi- self-supported catalysts (as compared to alumina-sup-
tal investments: ported catalysts) can enhance refinery margins by increas-
• Feed properties: controllable variables are feed source ing a refinery’s flexibility to process recalcitrant (for
(FCC naphtha and other naphtha streams), sulphur instance, resid-derived) feedstocks and extend run length.
species distribution, olefinicity, iso/normal ratios for In the past decades, applications of self-supported
paraffins, iso/normal ratio for olefins, FCC naphtha cut hydroprocessing catalysts started in diesel hydrotreating
points, and heavy tail composition. In one of our com- to increase diesel volume swell. More recently, self-sup-
mercial field tests, a refiner modified feed composition to ported catalysts have expanded into hydrocracking
reduce octane loss from 8 RON to 5 RON when making applications to make more or better chemicals, fuels, and
10 ppm sulphur gasoline. The change was implemented lubes. In addition, the superior hydrogenation activity
for normal Tier 3 operation. of self-supported catalysts enables better and flexible
• Splitter cut point: thiophenic sulphur should all be integration of varying refinery processes, resulting in
driven down into the HDS reactor while maximising C6- improved capital efficiency.
olefins in the overhead. Careful optimisation of this can As with supported catalysts, there are many different
save 2 RON octane versus ‘blind’ operation. self-supported catalysts, each with their unique chemical
• HDS reactor conditions: reaction rates of sulphur, ole- compositions, acid site densities, and pore size distribu-
fins, and aromatics are affected differently by changes in tions. Through its enhanced hydrogenation ability and
reactor operating variables and can by optimised using its carefully tuned pore structure, ART’s self-supported
modern analytical methods and models to improve ICR 1000 catalyst platform has debottlenecked refiner-
octane/sulphur performance. ies and hydrocrackers by enabling higher conversion of
• HDS catalysts: we have tested competitive FCC gas- vacuum gasoils (lower bleed rates), by enabling conver-
oline post-treating catalysts from Axens, Albemarle, sion of opportunity or synthetic gasoils, and by enabling
Haldor Topsoe, and a fourth supplier, side-by-side in a extension of hydrocracker run lengths. In addition,
multi-client catalyst testing program, and ranked them through its tailored acidity, ART’s self-supported ICR
on activity and octane/sulphur selectivity. Results are 1000 catalyst family has debottlenecked hydrotreaters by
available to anyone in Hoekstra Research Report 6. improving the quality and value of base oil, improving
• FCC catalyst technology: FCC catalyst and additives the quality of steam cracker feedstocks, enabling the sim-
directly affect the distribution of naphtha sulphur, ole- plification of white oil production, and increasing diesel
fins, and aromatic species. By looking at the FCC and production volumes.
its post-treater as an integrated unit, it is possible to
increase the reactivity of rate-limiting sulphur com- A Carl van der Grift, Director, Catalyst Intelligence,
pounds, increase the octane of the FCC naphtha, and vandergrift@catalyst-intelligence.com
reduce feed sensitivity to octane loss on hydrogena- Bulk metal catalysts (BMC) have a very high hydroge-
tion. This can have a bigger effect than selection of the nation volume activity and their use under optimised
post-treating catalyst. operating conditions can result in unique unit perfor-
• Capital investments: one of our refineries performed a mance not attainable with alumina-supported cata-
field test in 2017 showing unacceptably high octane loss lysts. The high hydrogenation activity is explained by
when making 10 ppm sulphur gasoline. They did a $20 the larger number of active sites as well as the higher
million revamp to reduce octane loss by 2.5 AKI with $27 intrinsic activity of these catalytic sites. This high
million per year benefit. This small capital investment hydrogenation activity is best deployed in the bottom
also enabled them to become a supplier of Tier 3 sulphur of the reactor to remove the most difficult nitrogen and
credits. Refiners considering investment in new units sulphur species and for deep saturation of aromatics.
should consider improved, 21st century gasoline desul- BMCs are used to alleviate conversion constraints in
phurisation technologies. existing hydrotreating or hydrocracking units to avoid
The above optimisation steps are enabled by use of the installation of extra reactor volume (capex). The
modern analytical methods, an industry-best octane extra hydrogenation activity in the unit can be used
model, and a process model that tracks the critical to process a higher intake of distressed feedstocks or
reactions affecting octane/sulphur performance, all to extend the cycle length at constant throughput and
of which were developed in a three-year, multi-client feed quality. In hydrocracking units, the BMC can be
research programme and are available to anyone at used to achieve high HDN and HDA in the pretreater
negligible cost by contacting george.hoekstra@hoekstra- and thus improve the performance (selectivity, cycle
trading.com, +1 630 330-8159. length) of the hydrocracking catalyst. The capability to

16 Catalysis 2021 www.digitalrefining.com

Q&A copy 27 (original).indd 7 23/02/2021 16:28

 T:210 mm

Austin Schneider
Director of Technology

Meet the
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T:297 mm
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 process distressed feedstock into high value products lysts may likewise be applied to improve hydrocracking
usually provides a good incentive for the use of BMC. yields of relatively high viscosity index base oils, due to
Some disadvantages of bulk metal catalysts may be: the superior aromatics hydrogenation activity.
(i) the relatively high purchase price, (ii) the long lead On the other hand, bulk metal catalysts may not be
time for fresh catalysts, (iii) the single-cycle use as they particularly advantageous from the perspective of a
cannot be regenerated/reactivated, and (iv) the loss of refiner with no access or otherwise very limited access
metal value as recovery of the metals is complicated to hydrogen-deficient, price-advantaged feeds and
when bulk metal catalysts are not kept separate from with hydrotreating capacity and capability to achieve
supported catalysts during unloading, such as during near-maximum volume swell with conventional, sup-
gravity unloading of a stacked bed. The loading dia- ported catalysts in any typical cycle.
gram needs to be designed by the catalyst supplier. The
catalyst supplier knows which operating conditions in A Per Zeuthen, Senior Director Europe, Haldor Topsoe,
the reactor are necessary for the BMC to show its high pz@topsoe.com
activity over the cycle. The increased bulk density of In the past, some bulk hydroprocessing catalysts were
the catalysts versus supported catalysts also requires well known for their high activities. However, the bulk
a calculation by the unit licensor to check whether the catalysts are very expensive – and they are known for
reactor support can handle the increased weight of the being non-regenerable.
catalyst load. Haldor Topsoe has recently developed a supported
catalyst with very high activity which outperforms
A Meritxell Vila, General Manager, MERYT Catalysts & the unsupported catalysts. This new catalyst, TK-6001
Innovation, mvila@meryt-chemical.com HySwell, has an improved performance stability and is
The great benefit of a bulk metal catalyst is that the sup- equally or even more active and regenerable than unsup-
port part of the catalyst, which is not catalytically active, ported catalysts.
is not present, therefore the volumetric activity is extraor- In other words, there are really no benefits of using
dinarily higher compared with a supported catalyst. bulk metal catalysts in hydrotreating.
This higher activity allows one to process more dif-
ficult feeds, to increase the flow rate of the unit, or to
extend the cycle length. Q What are the latest advances in FCC SOx reduction, and
The question is that the unit must be carefully studied what levels can be achieved?
and adapted to work with this kind of catalyst which
has a very high density and will require high hydrogen A Colin Baillie, Segment Manager, Environmental Additives,
consumption. As a consequence, compressors must be W. R. Grace & Co, Colin.Baillie@Grace.com
modified accordingly. Also, the temperature reactor pro- SOx reduction additives have long been recognised as a
file will change due to the high exothermicity of the reac- highly reliable and cost-effective option for controlling
tions, and hydrogen quenches should also be adapted. FCC SOx emissions. They are particularly suited for
These effects can be minimised by installing only one full-burn applications, where extremely low levels of
bed or two of bulk metal combined with beds of tradi- SOx (<5 ppm) and high levels of SOx reduction (>98%)
tional supported catalysts. can typically be achieved with additive usage of less
But it seems that the tendency for hydrotreating catalyst than 10% of fresh FCC catalyst rates. Although partial
next generations will be to become bulk metal catalysts, burn applications are more challenging due to the lack
in order to maximise their activity as much as possible. of oxygen being a rate-limiting step, high levels of SOx
reduction beyond 60% can still be achieved.
A Steven Zink, Principal R&D Engineer/Scientist, Honeywell The latest advance in FCC SOx reduction is the
UOP, Steven.Zink@honeywell.com launch of the EMISSCIAN SOx additive. This was the
The benefits of bulk metal catalysts in hydrotreating are culmination of an extensive research and development
determined by their degree of success to achieve cer- programme from Grace that included a multi-million
tain, economics-driven objectives. Bulk metal catalysts, dollar investment in SOx additive manufacturing facil-
known for their superior hydrogenation activity, have ities and the introduction of a new processing step. The
enabled some refiners to produce ULSD with assets that new process modification results in a more homoge-
would otherwise have been unable to produce ULSD, neous distribution of cerium and vanadium across the
avoiding the capital expense of reactor addition or the additive particle, as well as an optimised magnesium
requirement for an extra turnaround or reload. They aluminate spinel content. These improved features
have allowed some refiners to process a wider array of increase the effectiveness of the SOx additive, meaning
price-advantaged feedstocks, also without requiring an that SOx emissions can be maintained at lower additive
extra turnaround or reload. Where hydrogen is relatively usage rates, or if additive usage rate is maintained then
cheap, refiners make use of bulk metal catalysts with SOx emissions can be reduced further. The EMISSCIAN
price-advantaged, hydrogen-deficient feedstocks (for SOx additive has gained significant momentum in the
instance, light cycle oil) to maximise volume swell and market with more than 10 refiners switching from alter-
cetane, toward greater ULSD volume production and native products to this new technology.
for improved yields of light and heavy distillates from These recent successful case studies for the
hydrocracking conducted downstream. Bulk metal cata- EMISSCIAN SOx additive versus competitor additives

www.digitalrefining.com Catalysis 2021 17

Q&A copy 27 (original).indd 8 23/02/2021 16:28

 have been in both full and partial burn appli- Performance of EnviroSOx SOx reduction additive in FCC units
cations. For example, a full burn application
in North America saw SOx emissions drop Type of Sulphur Combustion Uncontrolled Controlled SOx PUF
from ca. 20 ppm to 10 ppm while also using a feed in feed mode SOx emission SOx emission reduction (kg-SOx/
lower additive rate, whilst a partial burn unit (wt%) (mg/Nm3) (mg/Nm3) (%) kg-additive)
in Europe saw the percentage SOx reduction Residue 2.8 Full 6800 2900 57 68
VGO 1.2 Full 2000 200 90 62
increase from 50% to >55% at a constant addi- VGO 1.8 Full 3000 850 72 45
tive addition rate. Residue 0.8 Partial 2500 1000 60 20
While other companies have begun to focus Residue 0.4 Partial 900 590 34 15
on investing in emerging technologies that
include next generation battery materials, as Table 1
well as technologies for producing hydrogen
and fuel cell components, Grace remains committed A Hongbo Ma, Technical Service Engineer, Additives, Johnson
to developing new FCC additive technologies for the Matthey, Hongbo.Ma@matthey.com; Carl Keeley, Regional
refining industry. To highlight this, we are making Sales & Key Account Manager – Refineries, Johnson Matthey,
another significant capital investment in our SOx addi- Carl.Keeley@matthey.com; Wayne Armstrong, Head of
tive manufacturing facilities in 2021, as we continue our Commercial Sales, Johnson Matthey, Wayne.Armstrong@
research and development activities to develop the next matthey.com
generation of additive technologies. Fluid catalytic cracker (FCC) feed contains sulphur
compounds. In the riser, the feed is converted to prod-
A Hernando Salgado, Technical Service Manager, BASF ucts and coke. Part of the feed sulphur deposits in the
Catalysts, hernando.salgado@basf.com coke on the catalyst. The catalyst is regenerated in the
There are several methods to effectively reduce SOx regenerator. In a full burn regenerator, the sulphur
emissions in an FCC unit, such as feed hydrotreat- is oxidised to sulphur oxides (SOx). In a partial burn
ment, wet gas scrubbers, and SOx reduction additives. regenerator, where oxygen availability is limited, part
While the first two solutions can reduce the emission of the sulphur is converted to reduced sulphur species
by 70-95%, they also involve considerable investments (carbonyl sulphide, for instance). Dedicated SOx addi-
and operating costs. On the other hand, the use of a tives are needed for each situation. Johnson Matthey’s
SOx reduction additive, such as BASF EnviroSOx, is a R&D has developed SOx additives specifically tailored
cost-effective solution that can be applied when a mod- for each application.
erate reduction is required. In full burn operation, a high concentration of sor-
EnviroSOx can capture SOx by using a MgO based bent is needed to capture sulphur trioxide. Johnson
material with enhanced retention, in order to maintain Matthey’s latest development has the highest concen-
its SOx capturing abilities longer than other SOx reduc- tration of sorbent available.
tion additives. In addition, a Ce based compound is In partial burn, where oxygen availability is limited,
added to promote oxidation from SO2 to SO3, together a specific oxidation package is needed to maximise the
with V2O5 which assists to achieve a full regeneration of conversion of sulphur to sulphur trioxide – without dis-
the MgO. As can be implied, the combustion mode of turbing the CO/CO2 balance.
the unit is one of the factors affecting the additive per- To control SOx emissions, refineries can reduce feed
formance; since nearly 90% of SOx is SO2 and a certain sulphur, use SOx additives, use a scrubber, or employ a
O2 excess is needed for it to be converted to SO3, partial combination of these. Refineries that have scrubbers can
burn units are more challenging. take advantage of SOx additives to reduce operating
Specifically, EnviroSOx has been successfully applied costs and reduce caustic consumption and waste han-
in a broad range of uncontrolled SOx concentrations in dling problems.
the flue gas up to 7000 mg/Nm3,
either in full or partial burn units.
100
One of the main parameters to
monitor the additive performance Refinery A
Refinery B
80
is the pickup factor (PUF), defined Refinery C
as the amount of SOx captured
SOx reduction, %

Refinery D
Refinery E
per mass of additive, expressed 60 Refinery F
in kg-SOx per kg-additive. In the Model
prediction
case of EnviroSOx, the PUF can 40
vary from 15 to 80, achieving SOx
reduction rates up to 90%, with 20
an average of 40-75%, depending
on the specific process conditions
0
and additive dosage in every FCC 0 2 4 6 8 10
unit. Some examples of using Regenerator flue gas CO, %
EnviroSOx in FCC units are pre-
sented in Table 1. Figure 1 Regenerator CO impact on SOx reduction

18 Catalysis 2021 www.digitalrefining.com

Q&A copy 27 (original).indd 9 23/02/2021 16:28

 ofAMeasure
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References
oils yield
With
and
byproducts
Such
reduction streams
heavy ofthis only
well-controlled
of which
crudes
depends the 5.6%.
approach, can
cracking
often
on Thus, the
build
optimised
the have the
focus
up
reactions
depth a heterogeneous
on ispartial
blending
high
of the analysing
that catalyst
viscosity,operations
occur burn catalyst
inissues
and
high the
(see in the previous
commercial
1upcoming
Christensen unit
P,requirements
Hearn using
A,higher Z-HD20. forfuture cleaning. Predictive ana-
exhibits
known result to both
cause aYeung
problem T, yield
The
such and for selectivity
as hydrocracking,
vibration for
ain
partmono-
abasedI, PTQ,
pump nisms were ins
which
upstream
salt
For
lytics
Q4 Figure
2017. amaximise
content, The
1).European
turns ainlagging
reactor,
high deactivation.
SOx the while use
concentrations
reduction
refiner
indicator all In
of operating
low
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into ofaFCC
cost
chlorides solids
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leading unit
refineryinplot
300 orthe typical
streams
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indicator two- are
and or borylated
compressor.
converted
asphaltenes,
on SOx catalyst
ensure to
concentration methane
poison
meeting Sonic
hydrochloric
high sulphur is
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monitors
organic
required
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levels,
CO can
The homogeneous
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specifications
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naphthenic
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gas, are:the catalyst.
in device
closest
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acidthe process safety.
stage
2andAmerican with
allows actionthe
Petroleumrecycle to be hydrocracker
Institute, taken before
Recommended having
lossesPractice a three-year
areUiO-67-Mix
incurred.
932-B, Design,
to
or andImportantly,
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regenerator when
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metals vibration
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Catalystexceeds
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giveaway)
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andAI orMACH
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Guidelines based for could
ana-
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organic+had no that
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severity hydroprocessing units, NACE International, Paper No. 04646, 2004.
in
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 (HC-AP), ex situ conditioning to control passivation 4. Finally, a refiner can save time during the sulphiding
of zeolite acidic sites. HC-AP does not require addi- process by ensuring all necessary equipment is on hand
tional passivation with nitrogen compounds during and ready to use. This includes having enough DMDS or
start-up. A risky hydrocracker start-up with in situ other sulphiding compound (with contingency), having
activation and passivation is made simpler and faster enough Draeger tubes, and having qualified personnel to
with Totsucat HC-AP. All types of Totsucat can also be take samples and analyse additional samples in the lab in
treated by Eurecat’s AirSafe process to temper self-heat- an expedited manner.
ing characteristics of the metal sulphides, allowing
Totsucat catalyst to be handled and loaded in air with- A Guillaume Vincent, Business Segment Manager HPC,
out the inert atmosphere normally required. Porocel, gvincent@porocel.com
Totsucat, CFP, HC AP, and AirSafe provide solutions Hydrotreating catalysts with metals in the oxide state are
to not only return units to operation much more quickly, inactive for removing sulphur or nitrogen from hydro-
but also to ensure the unit performs as expected. While carbon feedstocks. These metal oxides must be converted
well-controlled in situ sulphiding will deliver the to metal sulphides to maximise activity according to one
expected catalyst performance, not all in situ sulphid- of the following options:
ing procedures proceed as expected. Ex situ sulphiding • In situ sulphiding, which requires sulphiding agents
eliminates the risk of a less than ideal in situ sulphidation (for instance DMDS), heat, and hydrogen during the
and a unit which performs below expectation or must be activation
changed sooner than scheduled. • Ex situ preactivation (UltraCAT technology) which is
fully preactivated and ‘ready-to-use’
A Akash Moradia, Technical Service Manager, Advanced Legacy Porocel, which is now part of Evonik, specifi-
Refining Technologies LLC (ART), akash.moradia@grace.com cally developed UltraCAT preactivation to provide a
Catalyst sulphiding and unit start-up can add significant solution to convert oxidic catalysts in their sulphide state
time to a unit turnaround before normal feed can be while offering the following benefits:
processed. For many units, the time from introducing a • Provide full activity for temperature limited units
hydrogen atmosphere into the reactors to normal oper- (<600°F/<315°C)
ations can range from 2-7 days. There are several steps • Avoid temperature excursions and metal reduction
that can be done to minimise start-up time: during start-up
1. The most significant time saving is when the catalyst • Minimise H2S generation for downstream units sensi-
is pre-activated and has had cracked feed protection. tive to sulphur (noble metal catalysts)
Cracked feed protection eliminates the initial three-day • Avoid the use of sulphiding agents, long dry-out steps,
period after sulphiding when only straight run feeds and complicated in situ activation
can be processed. Also, catalyst pre-activation elim- • Provide cracked feed protection, which allows the
inates the catalyst dry-out step, in addition to the low introduction of cracked feed immediately after start-up
temperature and high temperature sulphiding hold For in situ sulphiding, the typical dry-out step under
steps. The catalyst dry-out can save approximately 4-12 hydrogen may last 24 hours and even up to 72 hours.
hours, while removal of the catalyst sulphiding steps This time is necessary to efficiently dry out the oxidic
can save ~6-24 hours. catalyst prior to ramping up the unit temperature and
2. If the catalyst is not pre-activated, using a low-LOI starting the DMDS injection, which typically lasts for an
catalyst (<10 wt% LOI) will provide significant time sav- additional 24 hours.
ings as well. Use of low LOI catalysts allows the refiner By using UltraCAT technology, your catalyst is deliv-
to heat up the reactor to ~350°F (177°C) prior to feed ered to your site fully preactivated and ready to use
introduction, which allows the reactor to reach minimum once the unit reaches the start of cycle temperature. With
pressurisation temperature (MPT) quicker while min- UltraCAT technology, there are no temperature holds
imising the time for catalyst dry-out
and feed introduction. This can save
400
the refiner ~4-12 hours depending on High sulphiding
the unit limitations. Comparatively, 350 temperature
SOC
high LOI catalysts (>10 wt% LOI) limit 300 SOC + 3 days
the temperature before feed-in to 240-
Temperature (˚C)

Low sulphiding if cracked stocks

275°F (115-135°C). 250 temperature
3. A refiner can also save 2-4 hours 200
once the feed has been introduced. Dry-out
150
Once the feed has gone through the
rectors and reached the separators, 100 In-situ
the reactor temperatures can be raised UltraCAT®
50
while the unit is still being flushed.
This allows the unit to be close to or at 0
0 10 20 30 40 50
low temperature sulphiding tempera- Time (hours)
tures when the feed is put into a recy-
cle loop. Figure 1 Time savings comparison between in situ sulphiding and UltraCAT preactivation

20 Catalysis 2021 www.digitalrefining.com

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 and no DMDS injection, which results in faster start-ups
with maintained optimal catalyst performances. The
technology offers a cracked feed protection which allows
refiners to gradually introduce the cracked feedstocks
immediately after start-up, whereas a three-day break-in
period is typically required for in situ sulphiding. A typ-
ical time savings comparison between in situ sulphiding
and UltraCAT preactivation is shown in Figure 1. CARELFLEX®
A Francis Humblot, New Business Developer, Arkema,
DRIVES
INNOVATION
Thiochemicals, francis.humblot@arkema.com; Vijay Srinivas,
Principal Scientist, Arkema, Thiochemicals R&D, vijay.srinivas@ Arkema’s Carelflex® service
introduces our new patent-
arkema.com pending in-line H2S Analyzer for
The catalyst manufacturer has a prescribed procedure to use with DMDS Evolution® E2

sulphide the catalyst. Any deviation from this procedure

H2S Analyzer designed
should be reviewed with the catalyst manufacturer and
for maximum:
approved. SAFETY – Fully enclosed
Spiked feed sulphiding of a metal oxide hydrotreat- RANGE – 0.03 - 5% H2S
ing catalyst is a process where a spiking agent such ACCURACY – No on-site
as dimethyl disulphide (DMDS) in the presence of H2 calibration
converts to hydrogen sulphide (H2S) in-situ, which then RESPONSE – Reading
reacts with the metal oxide to generate an active metal every 2 seconds
sulphide catalyst. This process being exothermic has to
be controlled by appropriate removal of heat to maintain
temperatures prescribed by the catalyst manufacturer.
Dimethyl disulphide (DMDS) is one of the most efficient PLEASE CONTACT US
sulphiding agents. With a high active sulphur content TO DISCUSS YOUR NEXT
CATALYST ACTIVATION
(68 wt%), it decomposes at relatively low temperatures
to generate H2S that reaches stoichiometric levels in the
DMDS decomposition at around 240°C.
All hydrotreating catalysts require a stoichiometric
amount of sulphur to be activated. The process of cata-
lyst activation involves sulphiding coupled with con-
trolled metals reduction. Knowing that the whole process
is exothermic, the rate at which the sulphiding agent is
introduced into the feed oil has to be controlled. Both the
sulphiding reaction and the reduction reaction are accel-
erated by increasing temperature. One needs to be cog-
nissant of the fact that there is a time delay between the
increase in DMDS flow rate and the concomitant increase
in reactor outlet temperature.
Below 240°C, the reduction reaction is not pro-
nounced and thus as we increase the sulphiding agent
flow rate in the temperature range of 220-240°C, we are
accelerating mainly the sulphiding reaction. For faster
sulphiding, one needs to have higher H2S concentra-
tions in the reactor while controlling the temperature.
This can be done by independent control of the liquid
feed rate into the reactor if feasible, and the sulphiding
agent flow rate into the liquid feed. Sulphiding is car-
ried out in two phases: primary and secondary. Primary
sulphiding is done at temperatures below 250°C and
secondary sulphiding is carried out from above 250°C
to >300°C or start of run temperatures (SOR) (>300-
350°C). Different sulphiding agents decompose dif-
ferently to H2S as a function of temperature. DMDS is
used extensively as a sulphiding agent because it starts
EU_A4_17_DMDS_01

to generate H2S at temperatures as low as 190°C and

decomposes exclusively to H2S and methane at tem-
peratures as low as 240°C. Maximising DMDS flow
rate above 220°C, ascertaining a controlled exotherm dmds.info

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 by intermittent changes in DMDS flow rate, while con- the void volume within the catalyst pellets to a mini-
tinuing oil feed, will allow for a quick breakthrough of mum and gives a homogeneous uniform fixed bed with
H2S (3000 ppm in the recycle gas). At this point after increased packed density. The approach of H2S reactant
breakthrough, DMDS feed needs to be continued to to the catalyst surface is greatly improved and the num-
establish a H2S concentration significantly higher than ber of metallic sites in contact can be maximised. This
3000 ppm in the recycle gas at a temperature of about allows a more complete, efficient, and shorter sulphiding
240°C. A vent of the recycle gas can then be taken, to step with reduced consumption of spiking agent, leading
purge the CH4 and some of the H2S*. Fresh hydrogen is to fully active catalysts.
then introduced to restore at least 60% hydrogen purity
of the recycle gas (the minimum value prescribed by the A Meritxell Vila, General Manager, MERYT Catalysts &
catalyst manufacturer). The H2S concentration should Innovation, mvila@meryt-chemical.com
still be significantly higher than 3000 ppm. There are three ways to presulphide a catalyst in situ:
After H2S breakthrough, the DMDS flow rate is liquid phase sulphiding with a sulphur spiking agent,
adjusted to maintain H2S, typically at 1.5-2.0% in the recy- liquid phase sulphiding with the unit feed, and gas
cle gas, while the temperature is increased by 15-20°C per phase sulphiding.
hour (or the catalyst manufacturer’s prescribed increase). Sulphiding with a sulphur spiking agent (this can be
Remember, as the temperature is increased, H2S is con- DMDS, DMS, DMSO, TBPS, TNPS, n-butyl mercaptan)
sumed to sulphide the catalyst. DMDS flow is continued includes the following steps: drying, wetting, first step
at a rate that maintains the H2S concentration well above sulphiding, H2S break-through, and second step sulphid-
3000 ppm. Once there is no more consumption of H2S ing. Normally, the complete process can take 24-36 hours,
and the temperature is >300°C, the catalyst is deemed to depending on the catalyst and unit conditions.
be completely sulphided and DMDS feed is stopped. The Sulphiding with the unit feed will include the drying
catalyst is sometimes soaked in recycle gas with high H2S step, wetting, and sulphiding, and because the concen-
concentrations at this high temperature for about an hour tration of sulphur is lower, this could take up to 2-3 days
or more. The recycle gas is then partially purged*, fresh to finish.
H2 is brought in, a value of H2S >5000 ppm in the recycle Depending on each catalyst (its quantity of active sites
gas ascertained, and the unit is prepared to accept sour to be sulphided), the duration of these steps can vary. It
feed in the production mode. is extremely important to follow the supplier’s instruc-
*All venting and purges require the amines gas treating unit to be tions regarding the presulphiding procedure, specially
on-line. referred to rates of temperature and flows, in order to
assure complete activation of the catalyst and to avoid
A Alain Rouquier, Consultant – Chemical expert, CREALYST- coking or undesirable reduction of metals.
Oil, ARouquier@crealyst.fr Regarding sulphiding directly with H2S (gas phase),
The metals contained in hydrotreating catalysts are typi- this would be the fastest way in situ, because the wetting
cally molybdenum with either nickel, cobalt, or tungsten step is avoided, and the active sulphidation agent, which
as promoters. The metal oxides are not active forms, they is H2S, is directly injected into the system. However,
must be activated by converting them to metal sulphides this procedure is not normally used at industrial scale
under a stable phase Co-Mo-S with the active species because H2S gas is not available and it seems that the
MoS2. The catalyst is sulphided by reaction of its active activity of the catalyst presulphided by this method is
metal sites with hydrogen sulphide produced, either lower than in the liquid phase.
in situ from a reaction between available sulphur in the There are also two ways to have the catalyst ex situ
feed stream and hydrogen, or more commonly from presulphided or activated that could save time in order
sulphur in a sulphiding spiking agent, usually DMDS or to start up the unit. With in situ presulphided catalysts,
DMS. The introduction of such a chemical is done with the catalyst pores are filled with a sulphur rich liquid
a volumetric pump to control the precise stoichiometric compound, which decomposes on start-up and converts
quantity of H2S generated. metal oxides into sulphides. With in situ activated cata-
Another method of presulphiding hydrotreating cata- lysts, the catalyst is already active, but the sites are pas-
lyst suggests contacting a hydrotreating catalyst with ele- sivated with a special compound that is released during
mental sulphur at a temperature below the melting point start-up. This last way is the shortest way to start up a
of sulphur – not often used industrially. hydrotreatment unit.
For catalytic reforming, it is known that hydrocracking
activity at start-up can be diminished if the catalyst is A Randy Alexander, Partner, Rector Resources LLC, randy.
sulphided prior to contact with the charge stock. alexander@reactor-resources.com
CREALYST-Oil, using its experience in solid particle In situ sulphiding of a fresh catalyst load will typically
handling and precisely in dense loading catalysts, sug- require 18-30 hours. While ex situ activation can shave a
gests refiners improve the sulphiding step, in efficiency few hours off of this process, the cost for ex situ treatment
and in time, by bringing homogeneity and uniformity to is typically 3-5 times higher than in situ sulphiding when
the catalyst bed to facilitate and increase contact between all of the extra expenses are taken into consideration.
H2S and the catalyst metallic phase by avoiding any These extra costs include bin rental for 3-6 months, deliv-
empty dead spaces around the solid. This process, using ery of empty bins to the processing site, return shipment
the technique of Homogeneous Dense Loading, reduces of empty bins, and catalyst losses due to fines. Catalyst

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 losses are caused by the additional handling of the mate- and a world that is cleaner for future generations, min-
rial (loading into the furnace, transfer of the material to imising disposal and designing out waste is essential.
a screening station, and unloading from the screens into And in many instances, it makes economic sense as well.
blanketed bins). Further, the sulphided catalyst is now Spent catalyst contributes significantly to the solid
softer and more fragile than oxide material. Loading this waste generated by our industry. Recovery of non-pre-
fragile material from the bins into the reactor results in cious metals minimises disposal costs. Three main driv-
additional catalyst erosion, shorter particles, and even ers determine whether recovery is economical: metal
more fines that can lead to pressure drop issues at start-up. value, transportation costs, and processing costs.
For in situ sulphiding, numerous steps can be taken to Metal value is determined by the market commodity
optimise the time required for completion of the process price. Currently, copper, nickel, and zinc products will
and to reduce the total cost. The first step is advance plan- typically generate a positive net value when recovered.
ning with the sulphiding service provider. This is critical Iron products generally result in a cost. Molybdenum
for avoiding delays in the start-up once the unit is ready could go either way, being very dependent on the cur-
for sulphiding. Advance communication regarding the rent pricing.
project details will ensure that the proper equipment is Transportation costs are dependent on distance from
brought on-site and that the personnel and sulphur spik- site to the processing facility and the amount of material
ing agent arrive on time. to be moved. If a site is remote, transportation costs can
In addition, utilisation of the following equipment will flip the economics of metal recovery. Also, if the spent
minimise sulphiding time while the catalyst bed is thor- catalyst has a lower metals content, the transportation
oughly and accurately sulphided: costs can be a dominant economic factor.
• DMDS/TBPS injection pump with web-connected Processing costs remain relatively stable. However,
telemetry: a web-connected pump (for instance, if heavy metals such as mercury, arsenic, or cadmium
SmartSkid injection system) allows engineers and oper- are present on the spent catalyst, recovery may not be
ators to continually monitor the critical parameters asso- feasible.
ciated with catalyst sulphiding in near real time. These Other factors to consider include the reduction in dis-
parameters should include injection flow rate, pressure, posal cost and TRI (toxics release inventory) recordings
recycle gas concentration (see below), fluid temperature, and shrinking resources of metals globally.
and valve position. By viewing this data on a secure web At Johnson Matthey, designing out waste with inno-
page, the chemical injection rate can be optimised to vative catalyst solutions is core to supporting this vision.
ensure the proper levels of H2S are maintained in the sys- Our patented Core Shell catalyst technology places active
tem while the reactor temperature is adjusted to appro- catalyst material where it is needed most and leads to
priate levels. intensification of the catalytic reactions within a flow
• Online H2S analyser: an online H2S analyser continually sheet. For example, Johnson Matthey’s KATALCO 57-6Q
monitors the H2S level of the recycle gas. This technique series of steam methane reforming catalysts has reduced
is much safer than using Draeger tubes for measuring the the active nickel metal by over half while still maintain-
H2S concentration, and real-time data from the analyser ing the performance customers count on. In addition,
allows the second temperature ramp to proceed without coated components offered by Johnson Matthey can
delay as soon as H2S breakthrough occurs. intensify a reaction while reducing the overall weight of
• Hydrogen purity analyser: a hydrogen purity anal- material used by over half in steam methane reforming
yser measures the gas concentration in real time. It is applications. Both solutions approach the recycling issue
important to keep the hydrogen concentration above by reducing the waste materials generated.
70% during sulphiding in order to maximise the kinetic The effects of the three main drivers determine if it is
rate of the sulphiding reaction. Maintaining an adequate economical to recover non-precious metals from spent
hydrogen level reduces the time required to complete catalysts. In addition, next generation catalysts are
sulphiding and also prevents premature coking in the being designed to minimise waste materials generated.
catalyst bed. Both support our industry’s commitment to environ-
Online monitoring of the sulphiding conditions aides mental sustainability.
in the decision-making process by minimising the time
lag waiting for or debating the accuracy of lab results. A Rahul Bhaduri, Consulting Engineer, Advanced Refining
Accurate control of the process also directly minimises Technologies LLC (ART), bhaduri@chevron.com
chemical usage. This can result in savings in chemical Spent catalyst economics are dependent on market
costs of up to 20-30% since only the minimum amount of conditions (metal prices), business value, and volume
spiking agent will be injected into the unit. through the recycler’s gate, operating expenses, and
an optimised processing stream. Currently (Feb 2021),
spent catalysts containing precious metals have signif-
Q Is it economically worthwhile to recover non-precious icant value to the recycler because of inflated precious
metals such as nickel from spent catalyst? metal (Pt, Pd, Au, Ag) market prices. Conversely, spent
catalyst comprising base metals (Mo, Ni, V, W, Co) has
A Susan Simpson, Strategic Sales Manager, Johnson Matthey, witnessed a considerable depression in metal values
Susan.Simpson@matthey.com over the past decade, resulting in reduced payback, if at
With the vision of a circular economy for our products all, by the recycler to their refinery customer. As is the

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 norm with most metal recyclers that
do not yield high value products (rho-
dium, iridium, osmium, and so on),
the ability to process high volumes
at low opex with superior recovery
is key to surviving an extended bear
market.

A Christian Bellino, Valorization Global

Product Manager, Eurecat, c.bellino@
eurecat.fr
The economics of recovery of base
metals from spent catalysts is depen-
dent on many factors. Each metal
and catalyst may have unique char-
acteristics, costs, and prices which Figure 1 Base metal catalyst recovery options
influence the economics of recovery.
Geographic and regulatory considerations can have a production. In general, recovery of spent catalyst met-
significant impact. Finally, there are the environmental als to a form suitable for reuse in fresh catalyst is not
aspects of a circular and sustainable economy to con- cost effective.
sider as a responsible corporate citizen. Eurecat actively participates in all the base metal cat-
Unlike precious metal catalysts, in which the metals alyst recovery options discussed here. They can advise
are usually recovered to their pure metallic state, base on the most economical approach to metals recovery
metals can be recovered in several different ways. Figure for each catalyst and application, and facilitate process-
1 shows the typical circular recovery options for base ing according to the recommendations.
metal catalysts. Disposal options are not shown and
should, in general, be minimised. A Carl van der Grift, Director Catalyst Intelligence,
The most common way to recover base metal cata- vandergrift@catalyst-intelligence.com
lysts is via regeneration and optionally rejuvenation. It depends on the Ni content, the nickel market price,
Limitations on recovery in this manner are usually and the presence of other contaminants such as water,
physical. To reuse catalysts following regeneration/ (hydro)carbon, sulphur, or other impurities which affect
rejuvenation, their particle length and strength should metal recovery and metal refining costs. In general, one
be high enough that there is no risk of pressure drop can say that catalysts with more than 10 wt% Ni can be
developing in reuse. Short particles can be removed recovered economically. On the other hand, even when
using special sieving techniques; however, the econom- the nickel cannot be recovered economically, it may be
ics of recovery will suffer if the yield of usable material wise to recover even the lower nickel content at a cost
is too low. The activity of recovered catalyst is often to avoid liabilities with the storage of spent catalysts.
close to fresh when proper techniques are applied. Several spent catalyst/metal reclaimers operate pyro-
If performance is a concern, recovered catalysts may metallurgical processes which will recover (part of)
be applied in lower severity units. In some cases, the the nickel and convert the alumina support into a non-
recovered catalysts may even be used in a completely hazardous, non-leachable slag. Such conversion by an
different service than originally applied. authorised waste company avoids future liabilities.
When catalysts become too short or weak for reuse,
the next best use is reshaping the catalyst into new A Mao Chen, Technical Sales Trader, TMS3 BV, mao.chen@
particles. There are many different options and applica- tms3.eu; Meritxell Vila, General Manager, MERYT Catalysts &
tions for reshaping. One of the most common uses for Innovation, mvila@meryt-chemical.com
reshaped catalysts is in guard reactors or beds. Activity When considering this question, it is difficult to limit
requirements are generally low for this service and they the response to a purely economic decision and disre-
are often sacrificial to trap feed contaminants. gard other factors which are gathering momentum as
Catalysts which have been poisoned by contaminant lead news items. Whilst environmental considerations
metals during operation are generally not recovered and protection may, on occasion, lead to an increase in
by regeneration/rejuvenation or reshaping and are the process lifecycle cost overall, the reputational value
best sent for metals recovery. Depending on the type and positive business profile benefits as well as the
of metal, concentration, metals pricing, and contami- moral obligation, whilst impossible to quantify in finan-
nant level, the cost of recovery can be partially offset cial terms, should not be underestimated.
by the value of the recovered products. In a few cases Increasingly severe natural disasters caused by global
(specific metals, high metal pricing, and/or very high warming and environmental management factors have
concentration), spent catalyst may even have positive meant that the consideration and implementation of
residual value. Since many of the base metals used in energy conservation initiatives, carbon reduction pro-
catalysis are also used in various metal alloys, they are cesses, and environmental protection have become
typically recovered as alloys or salts for use in steel critical.

24 Catalysis 2021 www.digitalrefining.com

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 Global refinery spent catalyst production has of powdered spent catalyst, followed by separation of
increased due to the processing of heavy crude oil iron as well as silica and other impurities, has achieved
which deactivates catalysts faster and shows higher extraction of 98% nickel.
metal and carbon deposition. Such spent catalysts are The recovered metals including Mo, V, Ni, Co, and Ni
classified by EPA as refining waste or hazardous waste, have enabled industrial applications for use as alter-
which are subject to stringent environmental regulations native raw materials for catalyst preparation and steel
regarding their disposal. Spent catalyst, provided it manufacture.
contains only Al, Si, and Fe, can be disposed of without Therefore, the spent catalysts recovery process is a vital
any special precautions or can be used in construction and viable option for waste recycling and reutilisation
materials. as it not only reduces reliance on natural resources with
The recovery of valuable metals from the spent cat- associated economic benefits but also reduces hazardous
alysts is an attractive option for their recycling and waste disposal loads.
utilisation. Accordingly, recycling methodologies and TMS3 supports this process by facilitating compliant,
eco-friendly cost-effective recovery processes have been efficient, and economic waste metal transfer transactions
investigated in order to minimise spent catalyst waste which contribute to streamlining the management bur-
which also reduces the environmental impact. den and overall process lifecycle cost.
One of the methods for this recovery, hydrometal-
lurgy, has been displacing inefficient pyrometallurgy
in many countries. Hydrometallurgy, also called the Q Please suggest an effective catalytic route for removing
leaching process, is a method of using leaching agents to carbon dioxide from our SMR hydrogen.
extract metals from spent catalysts. Soda roasting leach-
ing, basic leaching, and acidic leaching are all common A Tom Ventham, Sales & Technical, Europe and Africa, Unicat
hydrometallurgy processes. B. V. / G. W. Aru, LLC, tom.ventham@gwaru.com
Some experimental results showed that after roasting Hydrogen production is a complex, multi-unit process
spent Al2O3 based catalyst at 750°C for 30 minutes at an that must be optimised through the design phases to
Na2O:Al2O3 mole ratio of 1.2, the leaching recoveries of operation, to ensure it fulfils the objectives set out.
vanadium and molybdenum from the spent catalyst were Carbon dioxide is a by-product of SMR reforming reac-
both over 95%. tions. Carbon dioxide is also generated through the
A basic leaching process involves adding ammonium water gas shift reaction taking place in HTS, MTS, or
salts based solutions to previously ground spent cata- LTS reactors to increase hydrogen yield.
lyst, with a recovery rate of vanadium <96% and molyb- Post-processing of the SMR CO2 rich stream will
denum <95%. either happen using a PSA system to purify the hydro-
Acidic leaching of previously de-oiled, dried, ground, gen product and release CO2 as purge gas typically
and decoked spent catalyst can recover almost all metals routed to the reformer furnace or fuel gas network,
(Mo, V, and Co) simultaneously, with leaching yields of or a methanator to catalytically react CO and CO2 to
about 95%. In some acid leaching studies, the recovery methane using a nickel or ruthenium based catalyst.
rate of 97% was achieved by using organic acids such as In ammonia plants and other larger syngas production
oxalic acid and ethylenediaminetetraacetic acid (EDTA), units, a Benfield system can be found to remove CO2
whereas inorganic acids tend to have lower efficiencies, from the syngas stream. In terms of a purely catalytic
for instance with sulphuric acid, the recovery rate for route, the methanator catalysts Unicat can offer as part
vanadium and molybdenum was around 92%. of the MC-range are an attractive solution to refiners
Hydrometallurgical processes are also used for nickel looking to remove carbon dioxide from the SMR hydro-
recovery from spent catalyst. Sulphuric acid leaching gen stream.

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perfectly to your needs, to maximize profitability and reduce the
environmental impact of your processes.

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Q&A copy 27 (original).indd 16 23/02/2021 16:28

 Precious Metals
Edelmetale
Metale te cmuar
Qiymətli Metallar
Metal preziatuak
Dragoceni metali
Metalls preciosos
Bililhon nga Mga Metals
Zitsulo Zamtengo Wapatali
贵金属
Metalli Preziosi
Dragocjeni metali
Drahé kovy
Værdifulde metaller
Kostbare metalen
Altvaloraj Metaloj
Väärismetallid
Mahalagang Metals
Jalometallit
Métaux Précieux
Edelmetalen
Metais preciosos
Edelmetalle
Metali presye
Karfe mai daraja
Nā Metala kūpono
Lub Neej Zoo Nkauj
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11:57
 Tail gas hydrotreating in a high H2S gas plant
A tail gas hydrotreating catalyst delivers stable sulphur recovery operations, including
low emission levels and energy savings, with a low rate of deactivation

ZHANG XIAOGANG, WEI JINGHUI and ZHANG WENBIN

Sinopec

I
n the development of global oil long-cycling commercial applica- hydrotreating reactor. The heated
and natural gas resources, the tion of the tail gas treatment catalyst gas meets the surface area of the
Claus sulphur recovery process 234 developed by Shell Catalysts hydrotreating catalyst, the SO2 and
has become an important part of & Technologies in the Puguang elemental sulphur present in the
natural gas and refinery gas puri- Natural Gas Purification Plant. gas react with the reducing gas
fication.1 Because the total sulphur (hydrogen), and the carbonyl sul-
conversion rate of the Claus unit Process flow of tail gas treatment phide (COS) and carbon disulphide
is limited by chemical balance, the units (CS2) undergo hydrolysis reaction
sulphur recovery rate of the conven- There are 12 trains of sulphur recov- in the hydrotreating reactor. Tail
tional Claus process for two-stage ery units in the Puguang Natural gas leaving the hydrotreating reac-
catalytic conversion is 90-95%, and Gas Purification Plant. The design tor is cooled by the quench tower,
that for three-stage conversion can scale of each train is 200 kt/y, the then enters the tail gas absorption
only reach 95-98%. The Chinese operating flexibility is 30-130%, and tower. H2S present in the tail gas is
environmental standard GB16297- the annual operating time is 8000h. absorbed by the MDEA solvent, and
1996 Integrated Emission Standard In combination with the SCOT tail the tail gas at the top of the tail gas
of Air Pollutants strictly specifies gas treatment unit, the sulphur absorption tower enters the inciner-
the emission concentration and total ator. The tail gas is heated to 650°C
emission amount of SO2, according In the development of by heat generated from the com-
to which the corresponding total bustion of natural gas. The remain-
sulphur recovery rate of the sulphur global oil and natural ing low concentrations of H2S and
recovery unit must exceed 99.8%. COS in the tail gas are combusted
This can only be achieved through gas resources, the in the furnace and converted to SO2.
the use of a tail gas treatment unit.2 Other combustibles such as hydro-
In tail gas treatment, the SCOT pro- Shell Claus Off gas carbons, hydrogen, and CO are also
cess has been widely used due to its burned off at the same time. The
strong adaptability to Claus sulphur
Treating process has high temperature flue gas leaving
recovery units and high degree of become an important the furnace enters the incinerator
purification. The hydrotreating cat- waste heat boiler for heat recovery,
alyst used is the core of the SCOT part of natural gas generating medium pressure super-
process.3 heated steam, and the flue gas is
The Puguang Natural Gas and refinery gas discharged through the chimney.
Purification Plant of Sinopec The tail gas treatment unit has the
Zhongyuan oilfield is the biggest purification following process characteristics. A
ultra-high H2S content natural gas hydrotreating feed combustion fur-
purification plant in Asia and is also recovery rate can reach more than nace is used for a secondary oxida-
an important part of the Sichuan- 99.8%. The design SO2 content in the tion reaction to provide a heat source
East natural gas transmission pro- flue gas is less than 400 mg/m3. and a reducing gas required by the
ject. Based on a Black & Veatch The tail gas treatment section uses hydrotreating reaction. The semi-
design package, with Sinopec the hydrotreating reduction absorp- rich amine liquid of the absorption
Engineering Corporation as the EPC tion process to address sulphur tower is further used as a semi-lean
contractor, and with a design scale emissions. Tail gas from the sulphur liquid for the natural gas desulphur-
of 120×108 m3/y, it consists of six recovery unit enters the hydro- isation unit to save the steam energy
complexes. Each complex includes treating feed combustion furnace, consumption of solvent regeneration
two desulphurisation units, one mixes with the high temperature throughout the plant and, for full
dehydration unit, one sulphur flue gas generated by combustion utilisation of the waste heat of the
recovery unit, two tail gas treatment in the hydrotreating feed combus- unit, a hydrotreating reactor outlet
units, and one acid stripping unit. tion furnace, and is then sent to the cooler is arranged to generate waste
This article introduces the SCOT reactor, also known as the heat of the low pressure steam recov-

www.digitalrefining.com Catalysis 2021 27

cat shell.indd 1 23/02/2021 16:43

 Combustion flue gases Claus Tail gas
TGTU Incinerator
absorber steam drum
(C-402) (D-401)
Combustion air Hydrogenation
LP steam reactor (F-401) Quench
column
Semi-rich Incinerator
(C-401)
amine pumps (F-403)
Hydrogenation (P-402A/B)
reactor (R-401) Incinerator
stack
Quench Quench (F-403)
water pump water cooler
TGU water heat (P-401) (A-401) From P-102
exchanger
(E-401)
To main absorber

Figure 1 Process flow of the tail gas treatment unit of the Sinopec Puguang Natural Gas Purification Plant

ery unit. The tail gas incineration tion which is rapid and complete. until the H2S content at the inlet
section is provided with a high pres- Equations 5 and 6 are hydrolysis and outlet of the reactor showed
sure steam superheater; the waste reactions and are limited by thermo- the same value, the sulphiding pro-
heat generated by the incinerator dynamic equilibrium. cess was completed after condition-
is recovered, and the high pressure ing the catalyst for four hours. The
steam generated by the unit is super- Catalyst loading and presulphiding sulphiding procedure for 234 was
heated and sent to the system pipe The Puguang Natural Gas strictly followed to ensure that the
network (see Figure 1). Purification Plant carried out cata- catalyst would reach its optimum
lyst loading. Two layers of support- performance level.
Plant production ing ceramic balls were placed at the
Catalyst and main reactions bottom of the reactor. The catalyst Unit performance
The Shell C&T 234 catalyst exhibits bed was loaded with 234 catalyst to Analysis of daily operation
strong hydrotreating performance, a height of 1050 mm. On top of the The daily operation of the 234
with alumina as the carrier, and catalyst bed a thin layer of ceramic catalyst was analysed in terms
cobalt and molybdenum as active balls with a diameter of 13 mm was of catalyst activity, tail gas emis-
components. The main reactions of loaded (see Figure 2). sions, energy saving, and scope of
sulphur-recovered tail gas under the The fresh catalyst contains active application:
action of hydrotreating catalyst4 are: metal components in the oxidation Since start-up, the tail gas hydro-
state, and the catalyst needs to be treating unit of the Puguang plant
SO2 + 3H2 → H2S + 2H2O [1] sulphided for maximum hydrotreat- has run steadily for nearly eight
ing activity and stability, then the years. After loading and activating
S + H2 → H2S [2]
operating mode needs to be trans- of the 234 hydrotreating catalyst,
CS2 + 3H2 → CH3SH + H2S [3] ferred to applicable commercial a performance test run was carried
operating conditions. out. The inlet temperature of the
CO + H2O → CO2 + H2 [4] Acid gas containing H2S was used tail gas hydrotreating reactor is 250-
for catalyst sulphiding. The tem- 270°C, generally controlled at about
COS + H2O ↔ CO2 + H2S [5]
perature of the catalyst bed in the 250°C. At this temperature, the bed
CS2 + H2O ↔ COS + H2S [6] hydrotreating reactor was raised to temperature rise is healthy, the pH
240°C at the final sulphiding stage. of quench water does not decrease,
where Equation 1 is the main reac- Holding the temperature at 240°C and the concentration level of SO2 is
too low to be detectable, indicating
that the catalyst shows very strong
conversion.
Since the sulphide content can-
1. Sentry Support [Inert] 13mm, Sock
600 mm void
not be determined by conventional
chromatography when it is below
3. Sentry Support [Inert] 6mm, Sock 100 μl/l, gas chromatography with
2. 924 TL (3.2), Sock 2400 mm a flame photometric detector (FPD)
is used to detect trace sulphide in
the gas at the outlet of the hydro-
Support grid at 600 mm 4. Sentry Support [Inert] 13mm, Sock treating reactor to an accuracy of
0.1 μl/l. The detection results are
7350 mm
shown in Table 1 (average of 10:00
data collections per day for 10
Figure 2 Loading of the 234 hydrotreating catalyst days of full-load production of the

28 Catalysis 2021 www.digitalrefining.com

cat shell.indd 2 23/02/2021 16:43

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 Gas content at the inlet and outlet of the hydrotreating reactor φ, tion load fluctuations and equip-
ment working conditions, a single
Item 2011 2013 2015 2017
complex of the purification plant
Inlet, H2 (ψ), % 1.73 1.63 1.59 1.73 may operate under conditions of
Outlet, H2S (ψ), % 1.85 1.84 1.64 2.11 one desulphurisation unit (high
Inlet, SO2 (ψ), % 0.02 0.01 0.02 0.03 load), two sulphur recovery units,
Outlet, SO2 (ψ), % 0 0 0 0
Inlet, COS, ppm 100 100 100 100
and two tail gas treatment units
Outlet, COS, ppm <0.1 <0.1 <0.1 <0.1 (30-50% load). The hydrotreating
Inlet, CS2, ppm <0.1 <0.1 <0.1 <0.1 unit still functions well. The cata-
Outlet, CS2, ppm <0.1 <0.1 <0.1 <0.1 lyst performance is stable within a
space velocity range of 300-1000 h-1,
Table 1 the catalyst bed temperature dis-
tribution is even, and tail gas emis-
unit in each year, except 2015 data the hydrotreating unit. At lower sions are substantially lower than
before skimming). throughput, emissions reach a min- the design standard. This indicates
Table 1 shows that the SO2 con- imum of 192 mg/m3; at all times that the catalyst can maintain sta-
tent in the gas at the outlet of the this is lower than the design value ble hydrotreating performance and
hydrotreating reactor is extremely of 400 mg/m3 of SO2 emissions and hydrolysis performance under dif-
low, resulting in a reported value far lower than the national environ- ferent and sometimes challenging
of zero, indicating that the hydro- mental standard of 960 mg/m3. The load conditions.
treating activity of the catalyst is overall low emissions strongly indi-
high. The amount of SO2 entering cate that the catalyst gives strong Optimising operation
the quench tower is therefore very hydrotreating activity under current Since the 234 tail gas hydrotreat-
low, not impacting the pH of the conditions and its performance fully ing catalyst was put into operation,
quench water. The COS content at meets the demanding requirements optimised operating conditions
the inlet of the hydrotreating reac- of the unit. were applied to ensure that
tor is 100 ppm and at the outlet is Under full-load operation of extended catalyst service life could
below 0.1 ppm, indicating that the each train, the average tempera- be achieved.
hydrotreating catalyst has strong ture at the inlet of the hydrotreat-
hydrolysis activity. The CS2 con- ing reactor is controlled at around Stabilising Claus unit operation
tent at the inlet and outlet of the 250°C, the average temperature The air distribution of the Claus
hydrotreating reactor is indicated rise is about 26-31°C, the tempera- furnace and the temperature at the
zero because the CS2 concentration ture distribution of the catalyst bed inlet of the Claus reactor are closely
in the process gas is less than 0.1 is even, and the reaction is com- controlled to ensure that the hydrol-
ppm, already lower than the detec- plete and uniform. Compared with ysis rate of COS and CS2 in the
tion limit of the gas chromatograph other common tail gas conversion Claus unit is staged, and the load
FPD. processes where the temperature of the tail gas hydrotreating unit is
From December 2016 to January control index of the hydrotreating reduced.
2017, four of the 12 trains were cal- furnace is 278°C, the fuel gas con-
ibrated respectively. The total sul- sumption is reduced from an initial Adjusting furnace air distribution
phur conversion rate was above average of 610 m3/h to the current ratio
99.9%. 528 m3/h. Applying the lower fuel Affected by the online hydrotreat-
During normal production and consumption condition lowers the ing process, the hydrogen concen-
operation, the average mass con- inlet temperature to 250°C and at tration of the purification plant’s
centration of SO2 emissions of the the same time reduces the energy hydrotreating unit is lower than
incinerator is about 280 mg/m3; consumption and therefore lowers that of the refinery. At the begin-
this includes additional gas streams the opex. ning of start-up, when the sec-
other than the outlet stream of Affected by upstream produc- ondary oxidation ratio is too low
or the control valve for fuel gas/
combustion air fluctuates greatly,
Reactor operating temperatures, 2011 and 2018 it is easy to cause incomplete
combustion in the hydrotreat-
Unit Train-A Train-B Train-D Train-E ing furnace and produce carbon
Date Nov May Nov May Nov May Nov May deposits. The operator optimised
2011 2018 2011 2018 2011 2018 2011 2018 the process parameters, in this
Inlet T/°C 251.1 254.4 250.8 250.6 250.4 249.8 242.8 250.6
case the air distribution volume,
Top bed T/°C 260.9 283.1 269.5 273.4 266.3 269.6 261.9 271.2
Middle bed T/°C 263.2 283.4 271.8 273.2 266.2 268.2 267.2 271.3 by adjusting the air control valve
Bottom bed T/°C 262.15 283.3 271.4 273.6 265.7 269.2 272.2 271.3 PID of the hydrotreating fur-
R401 outlet/°C 257.3 277.4 267.1 271.1 260.2 266.7 268.8 268.5 nace and reducing the hysteresis
rate of the fuel gas and acid gas
Table 2 distribution. When the catalyst is

30 Catalysis 2021 www.digitalrefining.com

cat shell.indd 3 23/02/2021 16:43

 sulphided, the secondary oxida- References Zhang Xiaogang is Deputy General Manager
tion ratio of the hydrotreating fur- 1 Chen Gengliang, Xiao Xuelan, Yang of the natural gas treating plant of Sinopec
nace is increased to 0.85; in normal Zhongxi, et al, Claus Sulphur Recovery Process Puguang. He has been engaged for many years
in the research and production management
production, the secondary oxi- Technology [M], Beijing: Petroleum Industry
Press, 2007:1. of high sulphur natural gas treating and
dation ratio of the hydrotreating
2 Li Fazhang, Hu Hong, Li Yang, Low- purification.
furnace is adjusted to 0.78, which Email: 44024841@qq.com
temperature SCOT process for energy saving
reduces the carbon deposition and consumption reduction [J], Natural Gas
rate of the catalyst. At present, the Industry, 2009, 29(3): 98-100. Wei Jinghui is a Senior Engineer at the natural
pressure drop of the catalyst bed 3 Wang Jia Ming, Progress and application gas treating plant of Sinopec Puguang.
in the unit is only 6-12 kPa, which of SCOT sulphur recovery tail gas treatment Email: 3270780683@qq.com
ensures stable operation of the cat- technology [J], Nitrogenous Fertilizer
alyst under high space velocity Technology, 2011, 32(3): 7-13. Zhang Wenbin is a Senior Engineer and Chief
conditions. 4 Wang Kaiyue, Natural Gas Purification Technical Expert at the natural gas treating
Process [M], Beijing: Petroleum Industry Press, plant of Sinopec Puguang.
2005:339. Email: 28028999@qq.com
Catalyst deactivation analysis
The 234 catalyst showed stable per-
formance and a low deactivation
rate. Table 2 shows the reactor oper-
ation temperatures of the different
trains from 2011 to 2018. The over-
all impression is consistent when
comparing the data of the different
trains, even after seven years of
operation.

Conclusion Any catalyst, any weather, any time

Applying 234 tail gas hydrotreating
catalyst at the Puguang Natural Gas Driven by innovation for more effective services
Purification Plant turned out to be
a great success. The flue gas emis-
sions of the unit stay well below the
requirements of national emission
standards, enabling safe, stable, and
long-term operation of the unit. It Since 4 years successfully in operation in
meets the requirements for the use 7 countries in Europe and North America
of tail gas catalyst in the sulphur
recovery unit of a high H2S content Suitable for any loading processes and
natural gas purification plant, and all types of reactors and vessels
has delivered good environmental
and economic benefits. With further developments for material-
The 234 catalyst deactivation rate friendly convey up to 90 m above ground
is very low. After nine years since
start-up, the catalyst bed temper-
ature distribution and COS detec-
tion results show that the catalyst
still performs well enough to meet
requirements.
The long-term stable operation of
the 234 catalyst and its high activity BUCHEN-ICS has further developed its innovative Dense Phase Conveying
reduce the cost of catalyst procure- System to enable reactors to be filled with catalyst without the need for a
ment and in general lower opex. crane – no matter how strong the wind or how bad the weather.
Being able to operate at a signifi- A unique solution that makes it much easier for businesses to plan ahead.
cantly lower temperature reduces Safety guaranteed.
fuel gas consumption by more than
10%. Successful application of the Let us know what your requirements are!
234 tail gas hydrotreating catalyst
in the sulphur recovery tail gas
hydrotreating unit of the Puguang
Natural Gas Purification Plant pro- BUCHEN-ICS GmbH // Emdener Str. 278 // 50735 Cologne // Germany
vides a reference for other similar vertrieb.ics@buchen.net // buchen-ics.com // A company of the REMONDIS Group

large units in China.

www.digitalrefining.com Catalysis 2021 31

cat shell.indd 4 23/02/2021 16:43

magma.indd 1 23/02/2021 15:40
 Catalytic answer to a steam cracking challenge
Rapid growth in steam cracker capacity has encountered a developing problem –
contamination of opportunity naphtha feed by carbon disulphide

MARIE-CLOTILDE GOUVENOT and YOEUGOURTHEN HAMLAOUI

Axens

E
thylene is the most used mon- From cracking furnaces to
omer in the petrochemical
industry, employed as feed-
S downstream units
To understand where CS2 impacts
stock in several manufactures. Over the steam cracker operation, it is
the past few years, global ethylene worth bearing in mind the boiling
demand has grown rapidly. Asia, the point of CS2. This boiling point is
Americas, and the Middle East have S S close to that of some hydrocarbons
been leading new ethylene capacity with five carbon atoms (see Figure 2).
addition in the past decade. For the Downstream of the stream cracker
upcoming decade, China plans to Figure 1 Complexes are formed with furnaces, several fractionation steps
continue leading ethylene growth, carbon and CS2 target recovery of C2 (acetylene, eth-
with new steam crackers popping up ylene, and ethane), C3 (methylacet-
around the country. North America nel safety in case of exposure during ylene, propadiene, propylene, and
has also invested heavily in new extraction or even during transporta- propane), C4 (butadiene, butene1,
cracker projects in recent years due tion. H2S scavengers employed, such butene2, butane, and sometimes
to an advantage in ethane feedstock as triazine, amines, or formalde- vinyl acetylene), and the C5+ cut
supplied. Facing this unprecedented hydes, react with the carbon in crude (heavier components including aro-
competition, current ethylene pro- oil to form complexes. See Figure 1 matics as benzene and toluene).
ducers are exploring several options for example. As a direct consequence, CS2 is
to improve their competitiveness: In the furnace, these complexes are found in the C5+ cut. The C5+ cut
• Revamping ethylene capacity cracked to form CS2. may be used at several stages for dif-
• Improving refining and petro- ‘Heavy’ hydrocarbons present ferent purposes:
chemical integration problems for crude oil transportation • The C5 cut can be fully hydrogen-
• Using feedstock flexibility with or storage and, depending on their ated in a total C5 hydrogenation unit
diesel, crude, gas, or naphtha content, plugging can occur in the to recycle the C5 stream to the steam
• Using new feedstock sources wellhead and in storage. CS2 is then cracker furnaces and hence increase
Opportunity feedstocks offer used as a flow improver and found light olefins yield.
a main advantage of lower cost. in steam cracker furnaces. • C5 can be used in an extraction
However, each advantage often has It would appear that CS2 issues unit to valorise the isoprene cut.
a counterpart; these feedstocks come could be directly related to the naph- • C5+ can be treated as a pyroly-
with disadvantages. Among these tha source. Indeed, when importing sis gasoline (pygas) cut in a pygas
disadvantages, one has been identi- naphtha from Brazil, Canada, Egypt, hydrogenation unit to allow aromat-
fied over the years as a strong con- Kuwait, Morocco, Russia, and the ics (benzene, toluene) recovery while
taminant for downstream catalysts, US, operators often face this issue. removing the sulphur component.
carbon disulphide (CS2). Between the steam cracking fur-
Boiling points
naces and the C5+ cut, the CS2 con-
From well to steam cracking furnace tent becomes concentrated.
More and more petrochemical 44˚C Cyclopentene Therefore, 4-5 wtppm of CS2 in the
actors are facing high CS2 content naphtha feedstock will lead to 20-25
45˚C 1,2 Pentadiene
in the feedstock for their naphtha CS2 = wtppm of CS2 in the pygas feed, con-
steam crackers, and this tendency is 46˚C 49˚C Cyclopentane sidering typical pygas yield on the
expected to increase in the coming 50˚C 2,2 Dimethylbutane naphtha cracker (see Figure 3).
years. Indeed, crude wells are ageing This explains how CS2 has been
54˚C 4 Methyl-1-pentene
and, as a consequence, more H2S and identified by comparing the lack of
heavy materials like asphaltenes/ catalyst activity observed in C5 total
paraffins are present, making crude hydrogenation and pygas hydro-
oil extraction more difficult. Figure 2 Boiling points of CS2 and C5 genation with the origin/nature of
H2S could be an issue for person- hydrocarbons the naphtha feedstock.

www.digitalrefining.com Catalysis 2021 33

cat axens.indd 1 23/02/2021 16:45

 4 - 5 wt ppm in
Naphtha feedstock

Quench Tower
Fractionator
Steam

Caustic Tower
Stripper

Drier

Drier
Naphtha
with CS2

Fuel

Hydrogen Ethane Propane Butane

Ethylene Propylene Butene
Butadiene
Demethaniser

Depropaniser
Methane

Debutaniser
Deethaniser Pygas Treated
1st stage pygas

20 - 25 wt ppm in Pygas to Hydro

Concentration factor higher in C5 cut

Figure 3 CS2 concentration in the C5+ cut

CS2 impacts The strong poisoning effect of CS2 is indicated in the catalyst beds. The
Pygas feed may contain up to sev- has been observed in industrial units reactor exotherm distribution per
eral hundred parts per million of and confirmed by pilot tests. thermocouple is shown to the right.
sulphur. Speciation of sulphur, Indeed, in the presence of a few This exotherm distribution pro-
including CS2, has highlighted the ppm of CS2 in the pygas feed, a vides an accurate picture of catalyst
presence of thiophenes (80 wt% of reactor temperature increase is activity. Indeed, if the catalyst is
the total sulphur species), mercap- required to compensate the catalyst not inhibited, the exotherm should
tans/sulphides/disulphides (15 deactivation. be mainly present at the top part of
wt%), CS2 (5 wt%), and H2S/COS A pygas unit comprises two stages. the catalyst bed. If contamination is
(below 0.5 wt%). The first stage targets complete present in the feed, we observe cat-
These sulphur species have dif- removal of diolefin and styrenic com- alyst activity shifting from the top
ferent poisoning effects on the ponents while the second stage aims part of the catalyst bed to the bottom
catalyst used in C5/pygas hydro- at the complete removal of sulphur part.
genation. Among the sulphur spe- and olefin components while ensur- For the operational history sum-
cies described here, thiophenes ing lower aromatics losses. marised here, 9.5 wtppm of CS2 is
present the lowest poisoning effect, Figure 4 shows industrial feed- considered to be the initial instant
followed by mercaptans, sulphides, back from a first stage pygas unit T0, and the required styrene conver-
and disulphides in ascending order. operated with a palladium based sion is achieved with a 69°C of reac-
H2S/COS has the strongest poison- catalyst. This unit encounters CS2 tor inlet temperature (RIT).
ing effect and CS2 the second strong- inhibition on a regular basis. To the The CS2 level increases over the
est poisoning effect. left, the position of the thermocouple days of operation. At T0 + 6 days,
the CS2 content is around 16 wtppm;
however the styrene content is mul-
% DeltaT along catalyst bed
100
tiplied by more than 1.5 in the prod-
Tin uct, even with a 3°C increase in RIT.
90
Figure 4 shows that even a few
80
T1 parts per million of CS2 have a
DeltaT Distribution, %

T2 70 strong impact on catalyst activity.

60
Up to TW6 Nevertheless, the product is brought
Up to TW6
50 ~ 80% DeltaT
< 75% DeltaT back on-specification once CS2 is
Up to TW6
T3 40 < 65% DeltaT no longer present in the feed. This
T4 30 observation confirms that CS2 acts as
T5
20 a strong inhibitor for the palladium
T6
10
based catalyst. This industrial scale
T7
observation is also backed by pilot
T8 0
to to + 3 days to + 6 days test results.
Tout
Tin = 69˚C
CS2 = 9.5 wtppm
Tin = 70˚C
CS2 = 11.5 wtppm
Tin = 72˚C
CS2 = 16 wtppm Figure 5 shows the feedback from
a first stage pygas unit operating
DT1 DT2 DT3 DT4 DT5 DT6 DT7 DT8 DT9
with a nickel based catalyst. This
unit also encounters CS2 inhibition
Figure 4 CS2 impact on pygas palladium based catalyst on a regular basis. The weight aver-

34 Catalysis 2021 www.digitalrefining.com

cat axens.indd 2 23/02/2021 16:45

 age bed temperature (WABT) and
styrene in the product are shown for
0.48
several values of CS2 in the feed at a Reactor WABT, ˚C Styrene in product, wt%
constant operating flow rate.
The operating point of reference
corresponds to a product styrene 0.40
0.39

content of around 0.3 wt% with

WABT, ˚C
WABT ref
5.0 wtppm of CS2. From the initial + 12˚C
point to 9.0 wtppm of CS2, WABT WABT ref

is increased by 6°C to achieve 0.4

WABT ref + 7˚C
0.29 + 6˚C
wt% of styrene in the product. From
9.0 wtppm to 20 wtppm of CS2, the
WABT ref

nickel catalyst exhibits almost no

CS2 = 4.8 wtppm CS2 = 8.8 wtppm CS2 = 21 wtppm CS2 = 30 wtppm
deactivation.
At 30 ppm of CS2 in the feed, the
WABT needs to be increased by Figure 5 CS2 impact on pygas nickel based catalyst
12°C more than the reference WABT
while the product styrene is around In C5 hydrogenation and pygas Thermocouples are used in the cat-
0.5 wt%, which is above the maxi- hydrogenation, the challenge is alyst bed to adjust the reaction tem-
mum target content. quite different. As we have seen, the perature. Gas and effluent are sent
Industrial feedback shows that feed contains a wide variety of sul- separately to the same gas chroma-
activity is not recovered when CS2 phur species. The solution should tography system. An automated
is no longer present in the feed. The also be compatible with the catalyst control system is used to monitor the
catalyst is poisoned and a specific system. It was decided to develop sequences of test and analysis.
catalyst treatment is required to a new catalyst displaying the high-
recover its activity. est level of activity to ensure meet- Testing protocol
A clear conclusion emerges when ing the required level of styrenics/ Raw pygas feed rather than synthetic
the various observations are com- diolefins hydrogenation despite CS2 feed was used for this test, to adhere
bined. A nickel based catalyst, contamination. Once the first stage to industrial constraints in terms of
although it needs less temperature of pygas duty was achieved, the sec- styrene content and diene value. The
compensation than palladium to ond stage would then be efficient feed drums were blanketed under
resist CS2 contamination within the enough to remove CS2 along with nitrogen.
range 10-20 wtppm, nevertheless the other sulphur species from the Feed quality was controlled
tends to be poisoned by a high CS2 pygas feed. throughout the test’s duration
level. However, a palladium based A new palladium catalyst was as the pygas feed is known to be
catalyst is more active than a nickel developed focusing on this need for prone to ageing which leads to
catalyst and recovers its activity higher activity. In order to achieve conversion of cyclopentadiene to
more easily without any specific this target, the catalyst (LD 585) has dicyclopendatiene.
treatment. a very open pore structure under The sulphur level was low in the
Considering the relative activity an extrudate shape combined with raw pygas feed used for the test,
of palladium compared to nickel a fine distribution of palladium to with no CS2 present. This allowed
along with the observations reported maximise the accessibility of active more precise control of the CS2 con-
here, Axens decided to focus first on palladium and thus increase signif- tent and its effect on catalyst activity
the development of a specific pal- icantly the catalyst’s activity. by spiking CS2 in the raw feed.
ladium catalyst displaying enough Pilot tests were performed to
activity to ensure that it achieves the assess LD 585’s absolute level of Test methodology
required performance even at high activity and compare it to existing One mass balance was carried out
content of CS2 in the feed. Axens catalytic solutions. Some of the pilot per reactor per operating condi-
continues to develop the most suita- tests performed to validate LD 585’s tion at the end of each plateau.
ble solution for units currently using performance are described here. The effluent of each reactor is in
nickel based catalyst. mixed phase. The total mass bal-
Pilot studies ance is determined by comparing
CS2 contamination: solutions Unit description the reactor inlet (liquid phase) with
For isoprene extraction, Axens can A three-reactor isothermal plug a recombination of the reactor out-
propose a commercially demon- flow pilot test unit was used to let (mixed phase). The liquid mass
strated, adsorbent based solution compare the performance of dif- balance is determined by weight
which selectively traps CS2 from ferent catalysts. The reactors are in measurement and the gas mass bal-
the isoprene cut. The adsorbent effi- upflow mode, double piped, with ance by dry gas flow meter. Styrene
ciency is boosted by a feed composi- external high velocity thermal fluid activity and conversion are continu-
tion containing few types of sulphur used to guarantee a flat tempera- ously followed up with gas chroma-
species. ture axial profile in the catalyst bed. tography analysis.

www.digitalrefining.com Catalysis 2021 35

cat axens.indd 3 23/02/2021 16:45

 alysts displayed different levels of
100
activity.
90 The most active catalyst is the new-
80 est catalyst, LD 585, with the leading
Styrene conversion, %

70 palladium catalyst second and the

leading nickel catalyst clearly lower
60
in activity than both palladium based
Sequence 1
50
Low S content Sequence 4
catalysts, with conversion, respec-
tively, of 99%, 80%, and 10 %.
Sequence 2
40 High S content
Low S

The leading nickel catalyst, the

Sequence 3 content
30 Very high S content
leading palladium catalyst, and LD
20
585 were then settled in temperature
10 to achieve the same styrene conver-
0 sion before Sequence 2 began.
0 500 1000 1500 2000
Time on stream, h
Sequence 2 - high sulphur content
Leading Ni catalyst Leading Pd catalyst LD 585 Catalysts were tested with raw
pygas spiked with 50 ppm of CS2 for
Figure 6 Test results at different CS2 contents with raw pygas feed 100 ppm of total sulphur.
With CS2 at 50 ppm in the feed,
Catalyst characteristics for a palladium type than for a nickel sudden deactivation of the leading
In each reactor, 15 cc of Axens cata- based catalyst due to the higher palladium catalyst and the leading
lysts are loaded: activity of palladium catalyst. nickel catalyst was observed. LD 585
• A high activity nickel based cata- The temperature is controlled and maintained a good level of activity,
lyst (a leading Ni catalyst) adjusted to compensate catalyst with 50% styrene conversion instead
• A high activity palladium based deactivation following variation of of 100%, while the leading palladium
catalyst (a leading Pd catalyst) the CS2 content during the tests. catalyst could achieve only 20% sty-
• The new high activity palladium rene conversion and the leading Ni
based catalyst (LD 585) Test sequences catalyst achieved only a few percent
The objective of the test was to The test, carried out over 87 days, styrene conversion.
compare the activity level of each follows four successive sequences The temperature was adjusted in
catalyst proportionally to CS2 con- (see Figure 6). order to reach 90% styrene conver-
tent in order to maintain 90% styrene sion for all of the catalysts. Then, the
conversion. Sequence 1 - low sulphur content reactors were maintained at these
Taking into account the relative Catalysts were tested with raw operating conditions in order to test
activity of each type of catalyst, pygas at 50 ppm of sulphur in the the catalysts’ stability regarding
both palladium and nickel, the liq- feed (typical sulphur species from deactivation up to 1300 hours.
uid hourly space velocity (LHSV) is pygas feed – no CS2). LD 585 (red spheres in Figure 7),
identically set up in order to mimic The test required 300 hours of the leading palladium catalyst (blue
faithfully the industrial operating operation to adjust the operating triangles), and the leading nickel
conditions for the same reactor vol- parameters. Under raw feedstock catalyst (green squares) were quite
ume. Indeed, LHSV is usually higher stabilised conditions, the three cat- stable at this sulphur content with a
loss of activity of about 20%.
Under these operating conditions,
100 the leading palladium catalyst and
90 the leading nickel catalyst showed
80
good stability while LD 585 had the
Styrene conversion, %

lowest deactivation rate with almost

70
no decrease in activity.
60 Based on the deactivation rates
50 observed during Sequence 2, it was
40
decided to greatly increase the CS2
content in the feed.
30
20 Leading Ni catalyst
Leading Pd catalyst
Sequence 3 - Very high sulphur
10 LD 585 content
0
The catalysts were tested with raw
600 700 800 900 1000 1100 1200 pygas spiked with 350 ppm of CS2
Time on stream, h for 400 ppm of total sulphur. CS2
was injected into the three reactors at
Figure 7 26-day test at 50 ppm CS2 the same time (1400 hours). All three

36 Catalysis 2021 www.digitalrefining.com

cat axens.indd 4 23/02/2021 16:45

 catalysts showed strong and sudden
deactivation (see Figure 8). 100
For LD 585, styrene conversion 90
was 32% while the leading palla- 80 150˚C
dium catalyst’s styrene conversion

Styrene conversion, %
70
was only 20%. For the leading nickel 155˚C

catalyst, it was only 8%. 60 180˚C

The temperature was increased to 50 170˚C

achieve the highest possible styrene 40

110˚C
160˚C
conversion. For LD 585, the reac-
30
tor temperature was set at 150°C,
20 Leading Ni catalyst
which led to 95% styrene conver- 110˚C Leading Pd catalyst
sion (see Figure 8). With the leading 10 140˚C
LD 585
palladium catalyst, the temperature 0
was adjusted at 155°C to obtain 1400 1450 1500 1550 1600 1650 1700 1750 1800 1850 1900
Time on stream, h
70% conversion. For the leading
nickel catalyst, the temperature was
increased to 180°C (the maximum Figure 8 Temperature adjustment at 350 ppm of CS2
allowable temperature in first stage
pygas), with only 65% styrene con- rene conversion. Compared with the clear profile of this new contam-
version achieved; this was followed activity of the leading nickel catalyst ination emerged from joint work
by strong deactivation. At this level during Sequence 1, this corresponds between Axens and the customer.
of operating temperature, several to approximatively 1% of conversion CS2 acts as a strong inhibitor and
phenomena can occur, for instance loss per day, in other words 80% of arrives with naphtha feed from
sulphur penetration into the heart of total conversion loss during the test regions where crude oil is becoming
the nickel particles. The formation of sequences. The nickel based catalyst more and more difficult to extract.
Ni3S2 species, which are inactive in did not recover its initial activity Once in the naphtha, CS2 follows a
hydrogenation catalysis, can explain without special treatment once it had clear track from the cracking fur-
this decrease in conversion and operated with feed containing a high naces to the C5 cut and the pygas.
activity. amount of CS2. Once the origin and the nature of
The three reactors were left at The leading palladium catalyst the contamination are identified, the
these operating conditions. While achieved 70% conversion during most difficult part begins: determin-
the leading palladium catalyst and Sequence 4 with the same adjusted ing the best way to mitigate this seri-
the leading nickel catalyst showed operating temperature as in ous contamination.
almost 60% loss of activity with a Sequence 3. The leading palladium Axens worked on several solu-
sharp rate of deactivation, LD 585 catalyst recovered part of its activ- tions, focusing on removing CS2
demonstrated stability and main- ity once CS2 was no longer present from the naphtha feed or developing
tained a high level of performance in the feed, however catalyst deacti- a new catalyst displaying an ultra-
even with 350 ppm CS2 in the feed. vation here is quite important over high level of activity to compensate
time. The leading palladium catalyst for the inhibiting effects of CS2.
Sequence 4 - low sulphur content was in service for 87 days with high LD 585 palladium based catalyst’s
The catalysts were tested with raw CS2 fluctuations, which explains a high activity and stability are the
pygas at 50 ppm sulphur in the feed total loss of activity of around 70% first part of the solution developed
(typical sulphur species from pygas compared with the activity it dis- by Axens to address this worldwide
feed – no CS2) to determine recov- played at the beginning of the test. challenge.
ery of catalyst activity. Spiking of By contrast, LD 585 lost only 10%
CS2 was stopped at approximatively of its activity during the entire test. Marie-Clotilde Gouvenot is Global Market
2000 hours. Showing simultaneously high CS2 Manager with Axens, responsible for
This last sequence corresponds to resistance, excellent stability, and petrochemicals catalysts portfolio. She holds an
Sequence 1 (no CS2 and 50 ppm of activity recovery, LD 585 has demon- engineering degree from the Ecole Supérieure
total sulphur in the feed). The aims strated its efficiency in handling de Physique et Chimie Industrielle de la ville
of this step are two-fold: to deter- the CS2 issue through its ultra-high de Paris and a master’s degree in refining and
mine the capability of each tested intrinsic activity. petrochemicals from the IFP School.
catalyst to recover its initial activity Email: Marie-clotilde.gouvenot@axens.net
once CS2 is no longer present in the Conclusion Yoeugourthen Hamlaoui is a Catalyst
Technologist with Axens working on selective
feed, and to confirm that CS2 acts as Axens discovered the CS2 issue in
hydrogenation and reforming catalysts. He
a strong inhibitor. 2015 in discussions with a customer
holds an engineering degree specialising in
With feed conditions back to their facing unexplained loss of activity in chemical engineering and process engineering
initial level, the remaining activity a pygas first stage unit. This would from ENSGTI Pau and a degree in business
of the leading nickel catalyst was become a worldwide challenge for administration.
quite low, achieving only 10% sty- the steam cracker environment. A Email: Yoeugourthen.hamlaoui@axens.net

www.digitalrefining.com Catalysis 2021 37

cat axens.indd 5 23/02/2021 16:45

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Reactor resources.indd 1 05/03/2019 13:07

 Refinery’s performance confirms
catalyst testing
Commercial results from a naphtha reformer are a close match with data from
micro-pilot plant tests

TIAGO VILELA, NICOLAS POPOFF and MARK MOSER

Avantium

C
atalytic reforming is an impor- 3% hydrogen consumption), which ative tests means that the test results
tant process in the petroleum would represent an increased annual are reproducible and thus reliable for
refining industry. It is used to value of about €9 million. refineries to select the best perform-
produce high octane reformate for Avantium provides independ- ing catalyst for their operating con-
gasoline blending and high-value ent comparative catalyst testing ditions and feedstock. It is important
aromatics. The process objective is services to refineries to support to observe a catalyst’s performance
to convert petroleum naphtha frac- the catalyst selection process with in the commercial unit consistent
tions to high-octane aromatic hydro- actual key performance data. For with the performance obtained in
carbons as selectively as possible. this, we utilise a proven testing the pilot plant. This confirmation
Reforming also serves two other methodology and a high-through- obviously increases the level of con-
main purposes in a refinery: it is the put 16-parallel reactors micro- pilot fidence in the test results. In this
main hydrogen producer for use plant (Flowrence technology). The article, we present a comparison of
within a refinery or outside it; it also resulting data quality (precision, the key performance indicators, C5+
provides feedstock (predominantly accuracy, and reproducibility) yield, and hydrogen of a commer-
benzene, toluene, and xylene) for is continuously validated by the cial SR reformer with the Avantium
subsequent downstream petrochem- reforming catalyst vendors. micro-pilot plant test results for the
ical production processes. High data quality in these compar- selected catalyst.
Naphtha semi-regen (SR) fixed-
bed reforming units are operated at
NH2 MFC Microfluidic gas distribution + individual PI (Diluent)
relatively high pressure to mitigate
Drying (3A)
coke formation. As coke deposition H2+He MFC

increases, reactor temperatures are N2 MFC

raised to achieve the target octane. HT Microfluidic gas distribution + individual PI (Mixed gas feed)

SR reforming catalysts consist of H2 MFC

noble metals impregnated on an Coriolis Active liquid distribution system

alumina base, with a cylindrical or
Feedback

Low P N2 HT

spherical shape. Bimetallic catalysts

composed of platinum and rhenium Feed Drying
towers (3A)

are the most common type found in

a fixed-bed unit.
Feedback

The economic impact of changes

in yield with a SR reformer can be
significant. Assuming a 3000 t/d
unit, a shift from C1-4 to C5+ of about Reactors (I = 560 mm,
3 mm OD, 2.0–2.6 mm ID)
0.5% will result in an annual gain
in gross refinery margin of €800 000 Individual reactor heaters
(100–545˚C) blocks of 4 reactors
(3000 x 0.005 x 350 x €150/y). In the
case that a refinery is hydrogen con-
strained (for instance, the hydroc- N2 PIC
Vent
Active pressure control / Parallel pressure block

racker is throughput constrained (bleed)

due to a lack of hydrogen) this 180˚C

GC
value could be significantly higher.
Assume 10% higher hydrogen make;
that is roughly 8 t/d of hydrogen.
Effluent stove (max 170˚C)

This could enable processing some

265 tonnes more VGO feedstock (at Figure 1 Flowrence 16-parallel reactors high-throughput system

www.digitalrefining.com Catalysis 2021 39

cat avantium.indd 1 23/02/2021 17:04

 hydrocarbon breakdown for every
point in time. The baseline separation
Reactor 1 of ethyl benzene and all xylene iso-
Reactor temperature, ˚C

Reactor 4 mers, or the breakdown of the C1 to

C6 products, for example, are crucial
for economic and integration studies.
Thanks to the availability of multi-
ple reactors in the micro- pilot plant,
each catalyst system was tested in
10˚C triplicate reactors, in order to pro-
vide repeatability and confidence
intervals on the results. This greatly
0 50 100 150 200 250 300 350 400
increases the reliability of the test
Days on stream (DOS)
results.
Further than paper estimates, the
possibility to simultaneously com-
pare catalysts under various plant
conditions and with specific feed
Reactor temperature, ˚C

properties (amount of coke precur-

sors, presence of contaminants such
as sulphur, and so on) is thus critical
to determine the right catalyst.
SOR Accelerated deactivation EOR

10˚C
Comparison with refinery
commercial data
In order to compare commercial
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 operation data with the acceler-
Days on stream ated deactivation micro-pilot plant
test results, we need to look into
Figure 2 Data comparison window between refinery data (top) and the Avantium test the actual reactor temperature data
data (bottom) and make the comparison at simi-
lar change in weighted average bed
The micro-pilot plant test a short break-in period, the catalysts temperature.
The comparative test included four are tested at iso-RON (target octane
naphtha SR reforming catalysts level) and plant operating conditions C5+ yield
from different vendors, including – start-of-run (SOR), followed by an In order to compare the Avantium
the incumbent for benchmarking iso-RON accelerated deactivation test data with the refinery data, we
purposes. The pilot plant test was (increased severity) and then back to need to look at operating windows
performed in a fixed-bed 16-parallel plant operating conditions iso-RON with similar catalyst deactivation,
reactors high-throughput Flowrence (target octane level) – end-of-run approximately 25°C deactivation.
system (see Figure 1). (EOR). For this, we use the EOR Avantium
The performance of the catalysts In this article, we only present the test data between day 24 and day 26
(temperature required, C5+ yield, and micro-pilot plant test results from (days on stream, see Figure 2).
hydrogen production) is evaluated the catalyst selected by the refinery. Figure 3 shows a compari-
at fixed product severity (constant We do not present the results from son between the C5+ yield (wt%)
octane or research octane number, the other catalysts tests nor do we obtained in the micro-pilot plant
RON). The iso-RON operation is disclose the refinery’s name due to (Avantium test data) and the C5+
achieved by using an automated the competitive nature of the catalyst yield (wt%) obtained in the commer-
feedback loop between gas chroma- selection process and to respect con- cial SR reformer (refinery data): EOR
tographic analysis of the effluent and fidentially agreements with the cata- after 25°C deactivation for both, with
the reactor’s temperature, which is lyst suppliers. 95% error bars.
thus continuously adjusted. Figure 2 shows the reactor temper- As we can see, the difference
In order to simulate the commer- ature profile with time on stream. between the average C5+ yield
cial operation of the SR reforming The EOR data set in Figure 2 (bot- obtained in the Avantium test data
unit we need to perform an acceler- tom) shows approximately 25°C and the refinery commercial data is
ated deactivation protocol. It is nec- deactivation for the catalyst between consistent with a delta of 0.65 wt%.
essary to increase the test severity the fifth day on stream and the 24th We can also observe that the test
by accelerated deactivation to enable day on stream. data produced in the micro-pilot
performing such tests in a reasona- With continuous analysis of the plant is more stable with smaller
ble timeframe; it would not be eco- product effluent, these tests also standard variation than the commer-
nomically feasible otherwise. After provide refineries with a complete cial data.

40 Catalysis 2021 www.digitalrefining.com

cat avantium.indd 2 23/02/2021 17:04

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rezel.indd 1 23/02/2021 15:44

 C5+ wt% Refinery
C5+ wt% Avantium
±1.20%
±0.26% Δ 0.65 wt%
C5+ yield
(wt.%) Mean

Avantium base ± 0.26

Refinery -0.65 ± 1.20

1 wt% *The 95% confidence limits are ± 2 SD

200 220 240 260 280 300 320 340 360 380
Days on stream (Refinery)
24 26
Days on stream (Avantium)

Figure 3 C5+ yield comparison between micro-pilot Avantium test data and commercial SR reformer refinery data

Hydrogen production Avantium micro-pilot plant are very refining industry and holds a MSc in chemical
As a main H2 producer in the refin- consistent with those of the com- engineering from University of Aveiro and a
ery, the higher the hydrogen produc- mercial SR unit operation for the key professional doctorate in engineering degree
tion from the reformer the better. At catalyst performance indicators, C5+ from Delft University of Technology.
the Avantium micro- pilot plant, we yield, and hydrogen production. Email: Tiago.Vilela@avantium.com
can measure in real time the amount The Avantium refinery catalyst
Nicolas Popoff is a Project Leader within the
of hydrogen produced during the testing service provides a relia-
Refinery Catalyst Testing team. He has more
test. Similar to the C5+ yield, we also ble process (testing approach and than 11 years’ experience in catalysis, including
use the EOR Avantium test data micro-pilot plant) for comparing seven years of high throughput experience
between day 24 and day 26 (days on commercial naphtha reforming cata- at Avantium, and has been instrumental
stream) to compare the refinery data lysts to enable refineries to test mul- in developing naphtha reforming testing
and Avantium hydrogen wt% data, tiple options for their unit operating methods for comparing commercial catalysts.
both after 25°C deactivation (see [relevant] conditions. He holds a MSc in molecular chemistry from
Figure 4). The Avantium micro-pilot plant the University of Toulouse and a PhD in
The difference between the with 16-parallel reactors (Flowrence organometallic chemistry from the University
average hydrogen production in high-throughput technology) and of Lyon.
Avantium test data and refinery the methods applied, produce high Mark Moser is an independent consultant
commercial data is very small, which data quality (precision, accuracy, supporting Avantium since 2015. He has
is impressive for such a small wt% and reproducibility) which is highly extensive experience in testing, development
of hydrogen production. Here the important for comparative testing of and commercialisation of reforming catalysts
difference is just 0.10 wt% with very commercial catalysts. and is an inventor with 53 patents. With
stable data for both the test and the an extensive background in heterogeneous
commercial data. Tiago Vilela is the Director of Refinery Catalyst catalysis, surface science characterisation
Testing at Avantium, accountable for the techniques, product and process development,
Conclusion overall performance of the business line. He he holds a BS in chemistry from Hendrix College
The test results obtained in the has more than 18 years’ experience in the and a PhD from Northwestern University.

H2+ wt% Refinery

H2+ wt% Avantium
±0.18% ±0.18%
H2+ Prod.
Δ 0.10 wt% (wt%) Mean

Avantium base ± 0.18

1 wt% Refinery 0.10 ± 0.18

*The 95% confidence limits are ± 2 SD

200 220 240 260 280 300 320 340 360 380
Days on stream (Refinery)
24 26
Days on stream (Avantium)

Figure 4 H2 production comparison between micro-pilot Avantium test data and commercial SR reformer refinery data

42 Catalysis 2021 www.digitalrefining.com

cat avantium.indd 3 23/02/2021 17:04

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 Increased propylene from heavier residues
A specially developed catalyst enables a refiner to raise propylene selectivity from
heavier feeds at maximum feed rate

KUNIAKI MANABE Taiyo Oil Company

CAREL POUWELS, PAO SHENG WANG and TOMOCHIKA KOTANI Albemarle Catalysts

A
lthough the Covid pan- cal appraisal by communities with catalyst addition rate is flexibly
demic has diminished global regard to safety and environmental adjusted based on feed metal content
demand for refined products, issues. rather than on Ecat added metal con-
especially in transportation fuels in Taiyo aims to become a company tent. This helps achieve more stable
Asia and the Middle East, regional that achieves sustainable manage- performance.
demand for light olefins has contin- ment with the establishment of an The refinery team monitors FCC
ued to grow. Propylene, a building ‘integrated operating system’ that feed qualities and operational situa-
block for the petrochemicals sec- oversees activities ranging from the tions to ensure that the unit is always
tor, is one chemical gaining strong importation of oil to the manufac- operated to maximise profit and pro-
traction in demand. Propylene is turing and sales of petroleum and vide efficient operating conditions.
typically produced utilising steam petrochemical products. Both the This is accomplished by maximising
cracking and fluid catalytic crack- Shikoku and Yamaguchi Operations reactor temperature, maximising cat-
ing. The heart of gasoline producing have been certified for ISO 9001 alyst circulation, and optimising the
refineries, the FCC unit, has demon- (Quality Management System) RxCat system. Typically, the FCC is
strated versatility in producing and ISO 14001 (Environmental constrained by the regenerator tem-
widely variable yield distributions, Management System) and operate perature and LPG downstream flow
flexibility in handling a wide range with consideration for quality assur- rate. In 2019, Taiyo decided to take
of feed sources, and operating relia- ance, quality maintenance, and envi- on the challenge of processing heav-
bly with on-stream efficiency in con- ronmental preservation. ier feed to enhance unit profitability
sistently producing on-spec products Designed by UOP, the FCC unit within the existing unit’s limitations.
while maximising profitability. This at the Shikoku Oil Refining complex This meant that FCC unit delta coke
article describes the successful intro- operates RxCat technology and thus and LPG olefins selectivity needed
duction of Albemarle’s state of the is one of the most modern of FCC to be improved to overcome the unit
art residue-to-propylene FCC cata- units with the capability to produce constraints. Even before the intro-
lyst technology to Taiyo Oil’s opera- high volumes of propylene and pro- duction of heavier feed, however,
tions in Japan. mote conversion. Last year, Taiyo the regenerator dense temperature
celebrated 10 years of commercial could reach as high as 760°C. As
Taiyo Oil operation of its residue-process- such, the main challenges were to
Taiyo Oil Company, an integrated ing FCC unit. Since the FCC unit’s maintain maximum catalyst cooler
oil company in Japan’s Ehime pre- commercial start-up in November duty condition and to reduce regen-
fecture, produces high quality, envi- 2010, the operation has progressed erator temperature without sacrific-
ronmentally friendly petroleum towards greater efficiency with ing operational severity once heavier
and petrochemical products from revamps, more challenging process feed had been introduced.
its Shikoku and Yamaguchi opera- conditions, and operations against In short, Taiyo’s strategy is to
tions. The company has two crude the limitations of the process, thereby improve profitability by processing
oil distillation units of 138 000 b/d pushing the unit to enhanced output. a heavier resid feedstock, which is
capacity and one vacuum distillation more difficult to crack. In addition,
unit with a capacity of 30 000 b/d. Operations strategy this feedstock contains more metals
The company has worked actively Taiyo Oil’s FCC feed is 100% like iron, and propylene selectivity is
to upgrade, expand, and rationalise untreated residue, meaning that feed improved.
its operations to respond to differ- quality fluctuates more than usual in
ent demands for petroleum. While terms of Conradson carbon residue Typical solutions by operations
Taiyo Oil bears the responsibility of and in comparison to feeds hydro- Quite a few options are available to
maintaining supply and thus main- treated specifically with respect to handle the challenges of process-
taining the lifestyles communities the content of contaminant metals. In ing heavier feedstocks, given there
are accustomed to, as a handler of response to the feed’s characteristics, are no limitations in operations.
petroleum and petrochemical prod- the Taiyo Oil team developed a spe- Operators can choose to process
ucts, the company is subject to criti- cialised operations strategy wherein a heavier feed and then allow the

www.digitalrefining.com Catalysis 2021 45

cat albemarle.indd 1 25/02/2021 11:05

 regenerator temperature to increase Typical solutions by catalysts AFX, one of the catalysts founded
or run the cat cooler at higher duty, Taiyo has been using Albemarle’s on this technology platform, would
provided more air blower capacity AFX catalysts successfully since be a specifically good fit to address
is available. However, these actions the beginning of commercial oper- Taiyo’s challenges. Albemarle’s spe-
will potentially lower conversion. ation of the FCC unit in November cialists and research and develop-
In the case of Taiyo’s FCC unit, the 2010. Even though Taiyo met the ment team had conducted several
goal to process a heavier feed became design guarantees with AFX soon in-house studies to verify the feasi-
much more challenging as the unit is after the unit began operation, pro- bility of Denali AFX for maximum
limited by regenerator temperature, cesses and catalysts were continu- propylene applications from resid
cat cooler duty, and air blower capac- ously optimised through the years. feedstocks. These studies were posi-
ity. Reduction of throughput is one Throughput has been expanded in tive, and a unique Denali AFX cata-
solution; however, this option is typi- two steps by approximately 30%. lyst was designed for Taiyo’s specific
cally not economically desirable. Product slates were optimised while application. In parallel, a refiner in
While a heavier feed is more diffi- operation was tuned to maxim- Asia Pacific operating a heavy resid
cult to crack, it is also associated with ise output against unit limitations. FCC unit trialled Denali AFX suc-
an increase in deleterious metals such Albemarle worked closely with cessfully. This trial confirmed the
as nickel and vanadium. In Taiyo’s Taiyo to use the optimal catalysts in benefits that the catalyst exhibited
case, the worst impacts come from all these cases. in R&D, wherein better coke selec-
iron. While nickel and vanadium The AFX catalyst family is consid- tivity was one of the most important
enhance dehydrogenation activity ered an industry benchmark for FCC fingerprints. Based on all the avail-
and increase hydrogen and coke, iron applications that aim for maximum able information, Albemarle and
can have a dramatic impact on con- light olefins. AFX is suitable for pro- Taiyo’s technical staff agreed to trial
version and slurry yields. Moreover, cessing the heaviest residues and Denali AFX in the Shikoku Refining
their interactions with the catalyst achieving the lowest slurry while complex.
can hurt the morphology of the par- simultaneously delivering the high-
ticles. In addition to loss in the acces- est C3= yields and olefinicity. This Effective portfolio
sibility of catalyst particles, this can combination is key in most maxi- Albemarle’s technology provides a
lead to fluidisation problems. If a mum propylene applications as gas flexible, effective portfolio of tunable
FCC unit is diffusion limited or close handling is often limited. catalyst products. As part of these
to a diffusion limitation, an increase As outlined above, the latest cat- innovations, Albemarle developed a
in iron can be detrimental to opera- alyst change was driven by Taiyo’s zeolite system with enhanced meso-
tional reliability and performance. goal to increase profitability by pro- porosity and a novel matrix/binder
Apart from catalyst design solu- cessing even heavier feed. When system. These developments enable
tions, the typical approach to mit- feed heaviness increases, product a wider, more flexible formulation
igate iron poisoning is by utilising yields need to be maximised with window with enhanced binding and
a catalyst management system. As high conversion and low slurry improved zeolite stability, allowing
Taiyo has a wealth of experience yield. High propylene selectivity for catalyst formulation in a highly
with strong variations in iron con- in an LPG limited operation is also specific, focused manner. Thus, FCC
tent, the company has developed a important. A good understanding of operators can target every drop of
sophisticated catalyst management the chemistry involved is essential valuable product.
tool2 to diminish the potential for for the best catalyst design. Taiyo’s custom iteration of Denali
iron poisoning. In analysing the FCC Since the start-up in 2010, AFX AFX, the novel mesoporous zeolite,
feed as soon as possible, the catalyst catalyst had been reformulated and was designed by Albemarle special-
addition rate can be quickly adjusted optimised, and therefore helped ists to provide better stability and
accordingly. This tool enables Taiyo Taiyo to maximise profitability while improved coke selectivity. At the
to control catalyst activity as well as running against several operational same time, the applied mesoporous
unit conversion and slurry yields, limits. Now a step-out improvement zeolite was designed to be very low
resulting in more stable operation. was required. More metals tolerance, in hydrogen transfer activity. The
The third challenge involves max- better bottoms conversion, improved catalyst also includes the enhanced
imisation of propylene. Commonly, coke selectivity, and improved pro- activity of a metals tolerant matrix,
this can be approached by increasing pylene selectivity were all neces- thus allowing processing of feeds
the reactor outlet temperature and, sary. The catalyst also needed to be with higher metals.
where possible, through changing cost effective, and thus good activity Low hydrogen transfer5 is key to
feed preheat to maximise catalyst to retention was desirable. preserving light olefins, particularly
oil ratio. While a reduction in feed propylene. Like its predecessor AFX,
rate can also help increase propyl- Feasibility studies the low hydrogen transfer activity
ene yield, this is not often applied. In 2017, Albemarle launched its of Denali AFX is based on optimal
At maximum throughput and maxi- Granite technology platform, which balance of ingredients and assem-
mum reactor temperature, the high- appeared to be a potential solution bly technology, which provides very
est propylene volume is typically for Taiyo. Extensive screening and low hydrogen transfer. The assembly
obtained. evaluation indicated that Denali technology maximises catalyst acces-

46 Catalysis 2021 www.digitalrefining.com

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 sibility and accessibility retention,
which is key in propylene maximisa- 75
tion and high iron applications.3 This
makes the catalyst a promising next 70 AFX Denali AFX
generation catalyst solution for max-

Zeolite surface area, m2/g

imum propylene applications. 65
Many current and available max-
imum propylene catalysts with low 60
hydrogen transfer zeolites are less
stable and thus need higher catalyst 55
consumption or equilibrate at lower
catalyst activity. Bottom line perfor- 50
mance is thus penalised with less
45
propylene, lower propylene selectiv- May 19 July 19 Aug 19 Oct 19 Dec 19 Jan 20 Mar 20 Apr 20 Jun 20
ity, higher slurry yield, poorer iron
tolerance, and/or increased catalyst
addition rate. Figure 1 Proprietary mesoporous zeolite in Denali AFX enhances stability

Catalyst trial librium catalyst was properly con- catalyst which provides reliable and
Denali AFX was introduced to trolled and maintained at a similar flexible operation.
Taiyo’s FCC unit in mid-December level as the base catalyst AFX. These The new catalyst demonstrated
2019, with replacement reaching are positive markers illustrating the superior performance, which is
80% in mid-March 2020. Analysis contribution of the new zeolite that discussed in more detail below. In
of the equilibrium catalyst provides was applied in Denali AFX and an addition to meeting Taiyo’s objec-
evidence of the better stability of the indication of better stability. tives, actual performance was in line
zeolite applied in Denali AFX. While When refiners carry out a trial with with Albemarle’s projections for this
the fresh catalyst surface area is sim- a new technology, they are often operation.
ilar to the base catalyst AFX, the sur- concerned about the physical integ- One of the key goals of the catalyst
face area of the equilibrium catalyst rity of the new catalyst. Insufficient was to provide the ability to pro-
clearly increases (see Figure 1). This pressure build-up over slide valves, cess heavier feed via improved coke
difference in surface area is based on insufficient fines for fluidisation, selectivity. During the trial when
an approximately 50:50 split using increased catalyst losses due to attri- feed properties were heavier, the
the more stable zeolite versus the tion, or specifically too many fines regenerator bed temperature (RGT)
enhanced meso or matrix surface that end up in the slurry circuit are was successfully maintained below
area. all unwanted effects of any catalyst. the limit of 760°C. Denali AFX was
During the trial, the feed processed The change from AFX to Denali AFX able to process the heavier feedstock
was much heavier as the Conradson had a positive outcome and did not without hitting the constraint regen-
carbon residue content was sub- lead to any of these issues. Like its erator temperature (see Figure 3). In
stantially higher. Conradson carbon predecessor, Denali AFX is a robust fact, its use reduced delta coke and
residue has a strong tendency to
produce coke, which would nor-
mally lead to higher delta coke and 30 1
increased regenerator temperature at
AFX Denali AFX
equal cat cooler duty. Another indi-
cator of the heavier feed is the iron
content, which also increased sub- Feed-Fe Fe on Ecat
stantially with the equilibrium cat-
20 0.8
alyst (see Figure 2). During the AFX
period, feed iron averaged around 9
Feed-Fe, ppm

Ecat-Fe, wt%

ppm, whereas it increased to about

15 ppm during the Denali AFX trial,
with high values around 20 ppm.
This could potentially penalise the 10 0.6
activity and accessibility of the cat-
alyst, reduce unit conversion, sup-
press propylene yield, and lead to
higher slurry yields.
As Figure 1 shows, Denali AFX 0 0.4
equilibrated at a higher surface area May 19 July 19 Sept 19 Nov 19 Jan 20 Mar 20 May 20
despite the higher iron content.
However, the activity of the equi- Figure 2 During the Denali AFX trial, heavier feeds were processed with increased iron

www.digitalrefining.com Catalysis 2021 47

cat albemarle.indd 3 25/02/2021 11:05

 customers with unit monitoring.
Albemarle has modelled the Taiyo
770 FCC unit and applied it using oper-
AFX Denali AFX ating data compiled since 2014. As
760 a result, the company has been able
Regenerator temperature, ˚C

to study the differences in perfor-

750 mance between AFX and Denali
AFX through calibration and tuning
740 of the model and the various AFX
catalysts. The following results were
730 concluded:
• Better C3= selectivity; C3= increased
720
by 0.33 wt%
• Gasoline yield was slightly lower
710
as it was converted to C3= and C4=/C4
2 3 4 5 6 • Slurry yield was reduced by 0.23
Feed Conradson carbon residue, wt% wt% and increased liquid yield by
0.25 wt%
Figure 3 Denali AFX reduces regenerator temperature when heavier feeds are used with
higher CCR Operations
• Better delta coke selectivity equiv-
resulted in a drop in regenerator is substantially lower than usual. alent to 7°C reduction in regenerator
temperature by about 7°C. This was As Taiyo had operated its FCC unit temperature
obtained at equal cat cooler duty (see at similar reduced throughput with • Ability to process heavier feeds
Figure 4). AFX, a comparison could be made at within the maximum feed rate, ena-
In terms of performance, Denali similar conditions. bling Taiyo more flexibility in feed
AFX helped to improve the prod- Most refiners operate their FCC choice
uct slate. Owing to better coke units with some variations, and so
selectivity, a heavier feed could it is uncommon that feed and oper- Denali AFX value compared to AFX
be processed without hitting the ating conditions remain constant all • At constant feed quality, Denali
regenerator temperature limit. The the time. Therefore making a com- AFX delivers an incremental profit of
following main trends in yields parison between different catalysts $0.25/bbl
improvements were observed dur- can be challenging, and corrections • The throughput constraint is
ing the trial: increased propylene often need to be made so that a cat- relieved by lower RGT, offering
and propylene selectivity, increased alyst change can be compared at the another incremental profit of $0.11/
conversion, enhanced liquid volume, exact same conditions. FCC sim- bbl
and reduced slurry yield. ulation models are proven, useful
The trial took place during the tools to help in such evaluations. Conclusion
Covid pandemic, a period when Albemarle uses KBC’s FCC-Sim Taiyo Oil Company operates a
many refiners have reduced through- and applies this simulation model UOP RxCat FCC unit that processes
put as global gasoline consumption to study catalyst effects and assist untreated residue aiming at max-
imum propylene yields. In 2020,
Taiyo celebrated 10 successful years
770 of operation. Since the commercial
AFX Denali AFX start-up in November 2010, opera-
760 tions and catalysts have been con-
Regenerator temperature, ˚C

tinuously optimised. Throughput

750 has been expanded in two steps by
approximately 30%. Product slates
740 were optimised while operation was
tuned to maximise output against
730 unit limitations. Albemarle worked
closely with Taiyo to use optimal
720
AFX catalysts in all the above cases.
During this period, the catalyst has
been optimised several times to pro-
710
0 5 10 15 20 25 30 35 vide the most current and high per-
Cat cooler duty, Gcal/hr forming solutions for Taiyo.
To continue a profitable opera-
Figure 4 Denali AFX performs at reduced regenerator temperature at constant cat cooler tion, Taiyo made a strategic choice
duty to increase the heaviness of the

48 Catalysis 2021 www.digitalrefining.com

cat albemarle.indd 4 25/02/2021 11:05

 resid feedstock. As the refiner’s liquid volume. Albemarle esti- Kuniaki Manabe is General Manager – Refining
FCC unit is highly constrained, this mates that the new catalyst brings Department (Group-1 and Group-2) with Taiyo
decision required a step-out cata- an incremental profit of $0.25/bbl Oil Company Ltd. He participated in the RFCC
project for the Shikoku operations before going
lyst
ous to meet itsforgoals.
methods CO2 To meet these
disposal. CO2 when compared to AFX processing
AAG and SWAG.
challenges, Albemarle SWAGproposed almost to
on to serve as a Group Leader for Refining
the same feedstock. An additional Group-2 of Taiyo’s Refining Department, and
based enhanced oil recovery (EOR)
always
apply contains
and trial aDenali
substantialAFX, ammo-
its lat- profit 38 000
15.00of $0.11/bbl is obtained when later a General Manager for Refining 720
is a significant application of recov- Peak heat flux Group-2.
nia concentration, 55% NH3catalyst. in this

Peak tube wall temperature,

est 36 000
ered residue-to-propylene
CO2. CO2 based EOR involves relief in throughput constraint
Peak tube by Email: kn_manabe@mail.taiyooil.co.jp
wall temperature 700
example.
This The
catalyst mixed
was developed feed is 6.65%a
with lower34 000
regenerator temperature is Carel Pouwels is NG, $/MMBtu

Peak heat flux, BTU/ft2.h

pumping compressed CO2 through Global FCC Specialist Light
ammonia
proprietary on a dry
zeolite basis. An often Olefins with Albemarle Catalysts 680
to antechnology
oil-bearing that considered.
10.00
injection wells for- 32 000 in Amsterdam,
quoted
offers guideline is that the reaction
mation.enhanced mesoporosity
pressure inand The30 000
technology and design of The Netherlands. With extensive550 experience in
This restores the
furnace
improved effluent should be belowcon- 150
formation stability.
and forces The thezeolite
remaining Denali AFX is unique and the suc- the development and application of novel FCC
28 000
ppmv
tributes ammonia.
to better As Figure
coke 4 shows,
selectivity, one
5.00
cessful trial in Taiyo’s FCC unit has catalyst technologies, heH2,has $/kg640
held positions
oil toward production wells. It also
however,
of the key the NH
parameters levelneededcan tobeena-10 26 000
proven it to be a promising next gen-
in application research, FCC technical service,
mixes with the oil, expanding its
3 620
times
ble higher
the processingthan the recommended
of heavier feeds. In eration catalyst
24 000 for maximum pro-
sales, marketing, and business management. He
volume and reducing its viscosity. 0.00 currently holds the role of Global 600
FCC Specialist
maximum
addition, whenAFX
Denali very high levels
enhances metal pylene 22applications.
000
This enables it to flow more quickly Light Olefins. He holds a chemical engineering
of oxygen enrichment
tolerance, another are used
essential and
feature

ºF
through the porous rock of the 20 000 580
degree from Delft University of Technology.
the
for reaction furnace outlet is kept
oil such operations. Furthermore, it AFX, DENALI20and GRANITE40are marks of60 Email: Carel.Pouwels@Albemarle.com
80 100
reservoir. Injection of CO2 into Figure 6 Hydrogen price compared with natural gas price
at
is 2400°F. The
assembled problem
with high with high
accessibility Albemarle. O2 in enriched air, mol%
mature oil fields is increasingly con- Pao Sheng Wang is a Global Technical Service
ammonia
to minimise levels is the propensity
hydrogen transfer for
and Engineer with Albemarle Corporation, located
sidered the most effective method
ammonia
preserve to form ammonium salts
available light olefins like propylene, Figure 5 Effect of oxygen enrichment on peak heat flux and
in Taipei, temperature
Taiwan. With 24 in the waste
years’ experience
to revive output. References
in
whiledownstream
also coping equipment,
with very high most
lev-) heat boiler
12.0 in the FCC industry, he provides technical
Algae based carbon dioxide (CO 1 Amano T, Wilcox J R, Pouwels A C, Matsuura 10.8
especially
els of iron. in sulphur condensers 2 service to the Japan and Taiwan area, supports
sequestration has gained more T, Process
10.0 and catalysis factors to maximise
towards
The trial the end
started of the converter/ destruction in PTQ,
the Q3reaction furnace. special high efficiency
troubleshooting, and performs burners
unit from
health
interest due to itsinability
December 2019
to utilise propylene output, 2012, 17-27.
checks for Albemarle’s FCC customers and
condenser sequence. Ammonium Ammonia
2 Matsuura T,destruction
Bruno K, Hirokiis Taiyo FCC, A a reputable supplier are essential to
determined
8.0
Cost, $/kg

and was concluded to

produced CO2 as a carbon source, be successful. E, The
sales teams in the
5.8 Asia Pacific region. He holds
salts
Use cause
of Denaliincreased pressure drop, by reaction kinetics driven
story,by UOP ensure
three the reliability and operability
capacityAFX for demonstrated
“Three 6.0
Legged Stool” success 2013
its high CO2 fixation, a BS in chemical engineering from Cheng Kung
which
better reduces plant throughput and primary factors: the temperature of the SRU. Since the volume of the
and a cokefasterselectivity thanthan AFX con- and FCC & Merox Technology Users’ Conference. 3.4
growth rate 4.0 2.9 National University.
eventually
enables Taiyo (maybe
to be quite
more quickly)
flexible in within the E,reaction
3 Rautiainen Nelissen
2.0 furnace,
B, the res- reaction
Catalyst contamin- furnace is set by the exist-
ventional crop plants. The biomass 2.0
Email: paosheng.wang@albemarle.com
plugging
its choices ofoflines, and feeds.
heavier necessitating
Denali idence time in Engineering,
ation, Hydrocarbon the reaction Aprilfurnace
2003. ing equipment,
Tomochika Kotanitheis residence
an Account time is
Sales
produced can be used as a feedstock
plant
AFX shutdown to clear. (also
4 Yungshown in RFigure
K0Y, Jonker 4), and
J, Meijerink the determined
B, A novel by the flow rate through
for is a robust and reliableproducts
solution Manager for Albemarle’s catalysts portfolio,
other value-added methodSMR Coal catalyst Biomass Electrolysis Biomass-
For
with this particular case, since the mixing
and fast characteristics of the
to quantify FCCburner the furnace.
including FCC One way
catalysts, to increase
polymer catalysts
such as biofuels and chemicals.When
good physical integrity. accessibility, ACS 2002. gasification gasification microbial
SRU is
processing an existing
heavier plant and equip- being used. ammonia destruction would Based
(organometallics), and curatives. be toin
A hydrogen unitfeeds,
integratedit delivers
with 5 Pouwels C, The quintessence of FCC catalyst Tokyo, he holds a MS in biochemistry from
ment
better sizes are set,yield,
there are limited It is important to note that with allow the reaction furnace to oper-
a fertiliser unit using recovered pro-
propylene better CO2 design
Figure to maximize
7 Cost propylene,
comparison for ME Tech 2011,
hydrogen production
Kyushutechnologies
Institute of Technology,
techniques to increaseand
pylene selectivity, the ammonia
enhanced 13. levels of oxygen enrichment, ate
high at a higher temperature. This
Email: tomochika.kotani@albemarle.com

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www.digitalrefining.com PTQ Q4 2020 95

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cat albemarle.indd 5 25/02/2021 11:05
jmatthey.indd 1 23/02/2021 15:42
 More from the barrel
An alumina-supported catalyst for ULSD production or hydrocracking pretreat provides
longer catalyst cycles, higher throughput, and better product qualities

SERGIO A ROBLEDO and PER ZEUTHEN

Haldor Topsoe

T
he current pandemic has intro- Catalyst development
duced complications which Haldor Topsoe has for decades
refiners must contend with. been at the forefront of important
Lower jet demand due to less air technological breakthroughs in the
travel, along with overall less con- hydroprocessing industry. In the
sumption of transportation fuels 1970s, Topsoe discovered the active
due to lower mobility indices, CoMoS phase present in hydrotreat-
results in less than favourable refin- ing catalysts. In the 1980s, Topsoe’s
ing margins. In addition, the move researchers, led by Dr Henrik
towards green fuels will undoubt- Topsøe, discovered the difference
edly put additional pressure on the between Type I and Type II hydro-
refining industry in the years to treating catalysts and coined these
come. However, whether demand names, which are known through-
is high or low, the market still calls out the industry today. In the early
for high quality fuels. These tough 2000s, Topsoe’s commitment to fun-
market conditions mean refiners Figure 1 CoMoS corner sites are sterically damental research in surface science
are trying to squeeze as much value accessible for chemisorption paid off again, and a new activity
as possible from every molecule site was discovered: the brim site.
processed. ble products. As a result, a catalyst Using scanning tunnelling electron
In order to fare well, refiners that can maximise hydrogen uptake microscopes, researchers took pic-
must have all eventualities covered into hydrocarbon streams becomes tures of these new activity sites (see
when managing the molecules. The desirable and, generally speaking, Figure 1) which they named brim
market will dictate how much each NiMo catalyst has high activity for sites. With this finding, Topsoe
molecule of crude, or hydrocar- such a mechanism. Therefore, it is developed the BRIM technology
bon feedstock, costs and how many no surprise that worldwide market which fuelled the company’s growth
molecules of product are needed demand for higher activity NiMo through a leading catalyst portfolio.
and what their respective value is. hydrotreating catalysts is extraor- For years, BRIM and HyBRIM
Refiners need to have the flexibility dinary. Despite the tremendous catalysts have been relied upon by
to respond to these market changes improvements in catalyst technol- refiners facing challenges brought
and produce different products by ogy over the past 20-30 years, refin- about by clean fuels legislation,
either processing more barrels of a ers are still looking for the absolute maximising volume swell to reap
specific stream, increasing the boil- best NiMo catalyst for their ULSD increased profits from lower cost
ing range of the feed, and/or max- or hydrocracker pretreat reactors. hydrogen, or processing cheaper,
imising the barrels produced of a To avoid setbacks, refiners con- more difficult feeds. Building on
given product. The right hydro- tinuously need better, more cost- the experience from more than 500
processing catalyst can provide efficient, alumina based catalysts industrial applications of these cata-
this flexibility by having maximum with the highest possible activ- lysts, a new catalyst has been devel-
activity and providing the highest ity, in order to obtain the desired oped, TK-6001 HySwell.
volume swell. boost in performance and hydro-
Low natural gas prices, observed gen consumption. In addition, Increased activity
particularly in the US, result in alumina based hydrotreating cata- Topsoe’s latest catalyst technology,
low production costs for hydro- lysts will help minimise the oper- HySwell, involves an improved
gen gas. This low-cost hydrogen, ating cost when targeting volume production technique for NiMo
when catalytically added to middle swell by comparison with higher hydrotreating catalysts. It combines
distillate fractions, becomes very cost bulk-metal catalyst formula- the BRIM and HyBRIM technol-
profitable by increasing the liq- tions. This article will present the ogies with a proprietary catalyst
uid volume swell, which results in industrial performance of TK-6001 preparation step. Merging previ-
higher volumetric yields of valua- HySwell. ous technologies with novel, atom-

www.digitalrefining.com Catalysis 2021 51

Cat topsoe.indd 1 25/02/2021 11:10

 ic-level insights enabled Topsoe to Pilot plant feed properties Pilot plant operating conditions
design a metal slab structure char-
acterised by an optimal interaction Pilot feed Parameter Value
between the active metal structures API gravity, °API 31.6 H2 pressure 1370 ~ I 95 barg
with even higher concentrations Specific gravity 0.8676
Gas/oil ratio
7900 scf/bbl I
Distillation D2887 (°C/°F) 1331 Nm3/m 3
supported on the catalyst carrier. IBP 36/97 LHSV 3.34 hr ·1
The activity of the Type II sites is 5% 202/396 N slip 5-10 ppm
positively influenced by this inter- 10% 225/437
action between the metal slab and 30% 288/551
Table 2
50% 333/632
the carrier. HySwell technology 70% 372/702
exploits this combination of higher 90% 418/784 make progress in the development
concentration of active metals and 95% 438/820 of hydrotreating and hydrocracking
optimised interaction, substantially FBP 490/914
catalysts. HySwell technology is a
Nitrogen, wppm 376
increasing the activity of both direct Sulphur, wt% 0.27 direct outcome of this approach.
and hydrogenation sites, without Aromatics, wt% 31
compromising catalyst stability. Case study 1
Topsoe’s current NiMo catalysts Table 1 A US Midwest refiner operates a
have more than 500% higher activ- single-stage recycle hydrocracker
ity than the catalysts produced in to improvements in the required processing 17 000 b/d of vacuum
the mid-1980s. Figure 2 illustrates operating temperature. Topsoe’s gas oil and light cycle oil (LCO).
the progression in activity over scientists utilised tools such as elec- As part of the refiner’s catalyst
generations of catalysts for hydroc- tron microscopes, in-situ monitor- selection process when consider-
racking pretreatment applications. ing, and high-throughput screening ing replacing the incumbent cata-
The increased activity corresponds in their research programmes to lyst, Haldor Topsoe conducted a
pilot plant study using the reactor
scheme shown in Figure 3.
The feed properties for the pilot
1986 1995 1998 2005 2009 2013 2016 2018 plant are listed in Table 1. The pilot
plant tested the performance of
Relative volume activity

a combination of hydrocracking,
dewaxing, and post-treat catalysts
in R-2, and TK-609 HyBRIM in R-1.
The scheme chosen allowed the
refiner to see the individual perfor-
mance and impact of the pretreat
catalyst, and to measure nitrogen
slip versus required WABT and its
TK-525 TK-555 TK-565 TK-605 TK-607 TK-609 TK-611 TK-6001 impact on the hydrocracking cata-
BRIM BRIM HyBRIM HyBRIM HySwell
lyst. This is key information because
pretreat catalysts play a crucial role
Figure 2 Development of Topsoe’s hydrocracking pretreatment catalysts through four in determining final hydrocracker
decades product properties. The pilot plant’s
operating conditions are listed in
Table 2.
Feed Hydrogen
Industrial performance
Exit gas Based on these results, the refiner
ordered Haldor Topsoe’s catalyst
for the next cycle. In the period after
R1 R2 Naphtha product completion of the pilot plant and
the loading of the reactor, Haldor
Diesel product Topsoe launched its second gen-
eration NiMo HyBRIM, TK-611
HP Sep
HyBRIM. As a result of pilot plant
Stabiliser
Fractionator validation work, the launch of the
new catalyst, and the pilot plant
Interstage work for the unit, the refiner chose to
sample point
order TK-611 HyBRIM instead. The
UCO/lube new catalyst performed in the unit
as expected, even when the feed was
Figure 3 Pilot plant scheme heavier than feed tested in the pilot

52 Catalysis 2021 www.digitalrefining.com

Cat topsoe.indd 2 25/02/2021 11:10

 Typical unit feed and operating conditions

VGO feed
Sulphur, wt% 2.6
Nitrogen, wt ppm 950
Density, SG/API 0.91
IBP, °C/°F 295/563
50%, °C/°F 434/813
FBP, °C/°F 613/1135

Sim distillation, ˚F
Operating conditions
Temperature, WABT, °C/°F 377-422/711-792
Pressure, barg/psi 165/2425
LHSV 1.87

Table 3

plant (see Figure 4) and still main- 50% 90% 50% BP Pilot plant feed 90% BP Pilot plant feed

tained a low deactivation rate of

~1.0°F (0.5°C)/month (see Figure 5). Run day

Case study 2
An Indian refiner operates a sin- Figure 4 50% and 90% boiling point of feed
gle-stage hydrocracker processing
39 000 b/d of vacuum gasoils. In
the 2015 cycle loaded with Topsoe’s
hydrocracking and TK-609 HyBRIM
pretreat catalyst, the unit performed
quite well. For the 2019 cycle, the
refiner aimed to lower sulphur and Deactivation = 1.0 ˚F/month [0.5 ˚C/month]

nitrogen in the UCO and diesel

Temperature, ˚F

products.
Haldor Topsoe performed a unit
analysis and concluded that, for the
2019 cycle only, the pretreatment
catalyst needed to be replaced as
the highly active hydrocracking cat-
alyst still had plenty of activity left.
The target cycle length for the 2019
load was 36 months, while lower- Run day
ing product sulphur and nitrogen to
new levels. Topsoe recommended Figure 5 TK-611 HyBRIM WABT and deactivation rate
the installation of a split load of
TK-611 HyBRIM and TK-6001 ing in higher conversion and bet- higher volume swell creates a sig-
HySwell in the pretreatment reac- ter yields. In addition, it increases nificant economic advantage due to
tor, which achieved unit targets volume swell, due to an improved increased barrels produced. Most
while reducing catalyst costs. Due hydrogenation function. This often the value of such volume
to market conditions in the pan-
demic, the unit has been operating
with varying feed rates, while meet- VGO feed Test conditions

ing all unit margin objectives with Sulphur wt% 1.91 Temperature Targeting <30 ppm N
Nitrogen wt ppm 1500 Pressure, barg 140
significant savings for the refinery. Density SG/API 0.921 LHSV 1.15
Feed and operating parameters are 60.0 350
shown in Table 3. 50.0
Product nitrogen
300
Product sulphur

40.0 250
ppm N

200
ppm S

Economic advantage 30.0

150
TK-6001 HySwell’s improved activ- 20.0 100
ity can be used to lower reactor 10.0 50
temperature; increase unit through- 0.0 0
TK-6001 TK-611 TK-609 TK-6001 TK-611 TK-609
put; process cheaper, more difficult HySwell HyBRIM HyBRIM HySwell HyBRIM HyBRIM
feed; or, in the case of a hydro-
cracker, lower the nitrogen slip Figure 6 Data for hydrocracker pretreatment service for TK-6001 HySwell, TK-611
from the pretreat section, result- HyBRIM vs TK-609 HyBRIM

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 nificant value with least impact
VGO feed Test conditions on catalyst life. Table 5 details the
Sulphur wt% 1.91 Temperature Targeting <30 ppm N difference in feed quality when
Nitrogen wt ppm 1500 Pressure, barg 140 upgrading lower-value feeds. Figure
9 shows the lower WABT and,
Density SG/API 0.921 LHSV 1.15

0.8880
Product SG
50.00
Aromatics distribution more importantly, the same stabil-
45.00
0.8860
40.00
ity achieved with TK-6001 HySwell,
despite the increase in feed severity
0.8840
Specific gravity

35.00
0.8820
30.00 compared to the previous cycle with
0.8800
TK-611 HyBRIM. The improvement

wt%
25.00
0.8780
0.8760
20.00 in WABT can be as much as 25°F,
depending on feedstock properties
15.00
0.8740 10.00
0.8720 5.00
and unit operating conditions.
0.8700 0.00 For the second case study, the
Mono Di Tri+ Total
aromatics refiner achieved the goals of reduc-
TK-6001 HySwell TK-611 HyBRIM TK-609 HyBRIM VGO feed #2
ing product sulphur and nitrogen
in the UCO as well as in the diesel
products, while maintaining gross
Figure 7 Product specific densities and aromatics distribution before and after hydrocracking conversion of ~75%, by changing the
pretreatment with TK-609 HyBRIM, TK-611 HyBRIM, and TK-6001 HySwell catalysts pretreatment catalyst from TK-609
HyBRIM to a split load of TK-611
HyBRIM and TK-6001 HySwell. At
0.886 5.0 the same time, the unit achieved a
0.8837 Product SG Volume swell
0.884 4.8 significant volume boost due to the
increased hydrogenation activity of
Specific gravity

0.882 4.6
20% higher
0.880 4.4
the installed catalysts. In this case,
vol%

volume swell
0.878 4.2
0.8767
a combined load of HyBRIM and
0.876 4.0
0.874 3.8
HySwell can deliver higher profit-
0.872 3.6
ability while operating within the
TK-611 HyBRIM TK-6001 HySwell TK-611 HyBRIM TK-6001 HySwell constraints of hydrogen availability
and/or temperature rise. Figure 10
Figure 8 Obtained volume swell with HyBRIM and HySwell catalysts in a hydrocracker shows decreased nitrogen slip and
improved performance, resulting in
swell is significant and, in many TK-6001 HySwell delivered the improved profit margins.
cases, pays for the catalyst in a expected improvement in activity
matter of weeks. TK-6001 HySwell in an industrial application. In this Conclusion
can deliver these benefits and rival case, the higher activity was used to HySwell technology offers refiners
the activity of bulk-metal catalysts operate the pretreat section at lower with high-pressure ULSD units and
at a fraction of their cost. WABT than in the previous cycle hydrocracker pretreaters a strong
Case 1’s unit is now on its second with TK-611 HyBRIM, while main- hydrotreating catalyst solution. The
cycle using Haldor Topsoe cata- taining the same nitrogen slip. This higher activity of TK-6001 HySwell
lysts. Based on the successful run translates to a longer catalyst cycle compared to the second generation,
with TK-611 HyBRIM in the unit, and lower loss in profits due to less TK-611 HyBRIM catalyst, unlocks
and performance benchmark work down time. In addition, the refiner additional flexibility, which allows
(see Figures 6, 7 and 8), the refiner was able to upgrade heavier barrels units to obtain longer catalyst
chose to opt for the higher activity by increasing the FBP of the feed, cycles, process higher throughput,
of TK-6001 HySwell for its current when economics dictated, from deliver better product qualities, or
load. The current run’s basis feed 930°F to 1150°F (499°C to 621°C), process more severe feedstocks.
properties are listed in Table 4. enabling the refiner to capture sig- The simplest use of this improved
activity is being able to lower the
Midwest hydrocracker feed properties basis reactor temperature significantly,

Increase in feed severity possible using

Gravity, SG/°API 0.8602/33 TK-6001 HySwell
SIMDIST, °F 290/430/660/810/930*
(IBP/10/50/90/FBP)
SIMDIST, °C 143/221/349/432/499* Boiling point Increase from Cycle 1
Nitrogen, wtppm 300-400 to Cycle 2
Sulphur, wt% 0.3 T5O +30°F/17°C
Aromatics, wt% 32 T90 +5O°F/28°C
FBP +100°F/56°C
*Current cycle with TK-6001 HySwell has had periods of processing material with FBP as high as 1150°F (621°C).

Table 4 Table 5

54 Catalysis 2021 www.digitalrefining.com

Cat topsoe.indd 4 25/02/2021 11:10

 INDIA 2021
REFINING
TECHNOLOGY CONFERENCE
TK-6001 HySwell WABT TK-611 HyBRIM WABT
Temperature

Run day

Figure 9 Activity improvement between TK-6001 HySwell and TK-611 HyBRIM in an

industrial hydrocracker pretreat unit

30

N-Slip (2015 Cycle)

25 N-Slip (2019 Cycle)

20 20-21 SEPTEMBER
2021
N-slip, wt ppm

15
THE SHANGRI-LA,
10 NEW DELHI
5
CALL FOR PAPERS
0
0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 We welcome ideas for
Run day presentations on:

Figure 10 Product nitrogen from two cycles, in 2015 and 2019, loaded with TK-609 ➤ Hydrogen Management in
HyBRIM and TK-611 HyBRIM/TK-6001 HySwell, respectively
the Refinery
in both hydrocracker pretreat and the hydrocracker unit, resulting in ➤ Refining / Petrochemicals
ultra-low sulphur diesel service, substantially increased profitabil- Integration
while still obtaining the same con- ity. The higher activity of TK-6001 ➤ The Future for Fuels
version of sulphur and nitrogen. HySwell can also free up volume for ➤ The Digital Refinery
In addition, refiners must con- other functional catalysts, such as
sider how the additional activity dewaxing and/or de-met catalysts. ➤ Co-Processing with
can deliver economic advantages Renewables
beyond the unit itself. Processing Sergio A Robledo is a Senior Account Manager ➤ Carbon Capture, Storage
more difficult crudes in the refinery for Clean Fuels Catalyst Sales with Haldor and Application
or supplying better feed properties Topsoe in North America. He has over 20 years
➤ Next Steps in Energy
for downstream units can improve of experience in the refining industry and holds
overall profitability. Equally impor- a BE in chemical engineering from Stevens Efficiency
tant, the technology exhibits the Institute of Technology in Hoboken, New ➤ Oil to Chemicals
same high stability as BRIM and Jersey. Email: sro@topsoe.com
HyBRIM catalysts. Closing Date: 29 March 2021
Per Zeuthen is Senior Director of Product
TK-6001 HySwell catalyst has
Management with Haldor Topsoe. With
significantly higher hydrogenation
extensive experience in hydroprocessing
activity than TK-611 HyBRIM due catalysis fundamentals, he is a global advisor
to its higher activity in nitrogen for production, sales and marketing of
removal. This characteristic pro- hydroprocessing catalysts and technologies.
vides refiners with higher volume He holds a MSc in chemistry and mathematics
swell at similar operating conditions from the University of Odense, Denmark.
https://refiningindia.com
and offers increased flexibility of Email: pz@topsoe.com

www.digitalrefining.com RI 1/3 ad .indd 1 24/02/2021

Catalysis 2021 55 10:38

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 Increasing profit in hydrocracking and
diesel hydroprocessing
A drop-in catalyst for hydrocracking pretreat and distillate hydrotreating raises
activity with heat management savings

KEITH WILSON, LOUIS BURNS, DEAN PARKER and PADMINI LINGARAJU ExxonMobil
PIETER LUSSE, RENÉ SEVERENS and NATASJA BERG-SCHOUTEN Albemarle

I
ncreasing profitability is a key from 2000s with the Nebula bulk leading NiMo catalysts. Moreover,
question addressed regularly by metal catalyst. Celestia catalyst Celestia catalyst’s advantage arises
refiners, particularly in recent was first commercialised in 2015 from strong hydrodearomatisa-
times. In hydroprocessing terms, in a light feed hydrocracker and tion (HDA) activity that has been
and recognising that energy tran- improved the unit profitability via a demonstrated at over 2.5 times the
sition will mean limited scope for number of captured margin advan- level expected from leading NiMo
new build, increasing profitabil- tages. The catalyst has since been catalysts. Adding Celestia cata-
ity will focus on a simple ques- deployed in 15 process units in lyst to a catalyst load brings a high
tion: “How can we do more with North America, Europe, and Asia degree of activity improvement and
the facilities we already have?” An Pacific, demonstrating outstanding will improve performance signifi-
answer to this question will cer- hydroprocessing activity on light cantly even where it forms less than
tainly focus on selecting the right and heavy feeds, implemented 10% of the reactor volume.
catalyst solutions for use in an exist- across a range of hydroprocessing
ing refinery kit. Including Celestia platforms, and providing in each Defining the opportunity
catalyst in a catalyst system is a case a clearly defined opportunity Profitability can have many dimen-
drop-in opportunity to improve for increased profitability. sions, and examples where Celestia
unit profitability. This article describes the Celestia catalyst provides value include:
A refinery’s net profitability is catalyst, reviews three case stud- • Improve margin via feed basis
determined from a balance of con- ies where Celestia catalyst was change: increase feed rate, process
trolling opex in several dimensions: deployed successfully, and illus- less expensive and more refractory
feed costs, energy use, and use of trates how its applications can con- feed components.
utilities. The goal is to drive to the tribute to significantly improve • Improve margin via improved
highest margin for the amount of economic outcomes from a hydro- product quality and yield: lower
energy use. Older refineries may processing unit or hydrocracker. product sulphur or nitrogen, lower
be processing feeds that are sub- The case studies illustrate how product total aromatics, increase
stantially different in quality from application of Celestia technology volume swell, improve cetane and
the original design. This can lead in distillate hydrotreating, and light cloud properties, and improve
to units operating at lower utili- cycle oil (LCO) and vacuum gasoil conversion.
sation, or at higher energy use to (VGO) hydrocracker pretreat appli- • Reduce operating expense: stretch
meet a sub-optimal product slate. cations has yielded exceptional a unit cycle length, eliminate a unit
The choice to include new capital margin and operating expense shutdown to coordinate with refin-
to improve the operating efficiency returns. ery wide shutdown planning.
is rarely justified, particularly in • Reduce energy consumption:
the current environment, thereby Celestia catalyst change the reactor temperature
leaving the refinery margin also at The catalyst’s performance is profile to reduce inlet temperature,
sub-optimal levels. What if there is brought about by increased or/and increase outlet tempera-
another way to unlock performance hydrodesulphurisation (HDS), ture, leading to reduced energy
in existing equipment? hydrodenitrogenation (HDN) activ- consumption.
Celestia catalyst is a novel bulk- ity achieved through a unique
metal catalyst co-developed by design. The catalyst is a bulk-metal Heat release management and
Albemarle and ExxonMobil. The design synthesised almost entirely energy sparing
goal of the catalyst design was from the active metals needed for Adding significant activity to the
to drive catalyst activity to new hydroprocessing activity. This reactor does come with additional
heights to enable new use of exist- enables much higher activity than considerations. Hydroprocessing
ing equipment in ExxonMobil’s conventional catalyst, more than reactions are generally exothermic
refineries. This continues a trend twice the volumetric activity of in nature and lead to temperature

56 Catalysis 2021 www.digitalrefining.com

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 rises in the reactor catalyst beds.
Celestia catalyst is certainly more
Quench gas
exothermic than other catalysts and
Reactor 1 Pretreat Reactor 2 Hydrocracking
the catalyst temperature rise needs
to be managed to ensure process
and product quality control, and to
minimise catalyst deactivation.
ExxonMobil has developed Recycle gas
mitigation strategies to manage
Recycle gas
safely the operation of the catalyst. preheat furnace
Celestia /
Mitigations used to control catalyst Duty 15 MW
Nebula
temperature rise include: catalyst

• Splitting the Celestia catalyst load

Feed
between beds to limit the tempera- preheat
ture rise per bed. VGO feed
exchanger

• Increasing inter-bed quench

gases. Cold quench gases are intro-
duced between catalyst beds and Figure 1 Once-through hydrocracker configuration
mix with the hot liquid and vapour
exiting the bed above. load is maximised within the unit provides external energy to preheat
• Changing the reactor tempera- facilities capability and design. the combined hydrogen gas stream
ture control strategy to increase the Improved outcomes created by which is blended with the feed prior
ascending temperature rise axially Celestia catalyst will also be varia- to entering the pretreat reactor (see
in the reactor, accomplished by ble but generally complementary to Figure 1). The reactor inlet tempera-
reducing the reactor inlet temper- the process unit’s economic targets, ture controls the degree of furnace
ature, or increased outlet tempera- and also can generate value across firing required.
ture, or both. the site’s business. A 1:1 Celestia/Nebula catalyst
• Limiting the start-of-run opera- 2. Optimising Celestia catalyst load system was loaded into bed 3 of
tion to lower reactive feeds over one to achieve a predefined process a three-bed pretreat reactor. This
or two weeks during the catalyst objective: in this case, the load is replaced a Nebula/NiMo cata-
line out period. prioritised, determined to achieve lyst load used in the prior cycle.
Placement of Celestia catalyst is process advantage and economic The process objective achieved by
a critical component to the cata- objectives. The application may the Celestia catalyst addition was
lyst stacking design, and typically require limited investment to fully to increase margin by maximising
it would be loaded in mid to lower mitigate heat release, heat integra- the rate of a refractory heavy coker
catalyst beds. This strategy allows tion, or hydraulics impacts. gasoil processed in the mixed VGO
the catalyst to work efficiently, Each of the value creation opportu- feed. The Celestia catalyst load met
removing the more refractory sul- nities illustrated has been realised by the economic objectives, more than
phur and nitrogen species, and incorporating Celestia catalyst into a doubling the heavy coker gasoil feed
enhancing aromatic saturation. reactor load. They are illustrated by processed compared with the prior
A hydroprocessing unit config- the three following case studies. cycle while reducing the nitrogen
uration (hydrocracker or hydro- slip to the hydrocracking catalyst
treater) and design will vary with Case 1: Increased feed margin and beds. Celestia catalyst improved
core business purpose. While reduced energy consumption in a product qualities and demonstrated
Celestia catalyst is an enabling VGO hydrocracker high aromatic saturation and HDN,
influence to improve profitability, The first case study begins with a which boosted the cracking cata-
the extent of the gain in opportunity once-though VGO hydrocracker lyst’s functionality and led to sus-
will depend on the unit configura- application that converts a heavy tained conversion levels. Celestia
tion and facilities design. VGO feed to clean fuels and steam catalyst also improved the density of
cracker feed. The unit comprises a the export unconverted oil stream,
Implementation pathways and case two-series reactor system (pretreat providing economic credit to a part-
studies and cracking reactors), with recycle ner refinery steam cracker.
Considering the above, the gas and hydrogen make-up gas. The An energy consumption credit
approach taken to achieve oppor- reactor feed is preheated against was not originally included in the
tunities for profitability in 15 appli- cracking reactor effluent in several economic forecast for deployment
cations to date has broadly fallen heat exchangers, with the final shell of Celestia/Nebula catalysts, but
into one of the two implementation preheating against the inter-reactor the Celestia catalyst’s impact ena-
pathways: stream. This exchanger is bypass bled significant value to be captured
1. Optimising Celestia catalyst controlled to achieve the cracking from reduced furnace firing. The
load to predefined equipment lim- reactor inlet temperature required reactor operates an ascending tem-
itations: in this case, the catalyst for the unit conversion. A furnace perature profile; the reactor inlet

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 temperature and the beds 1 and 2 exotherm advantage at start of run
temperature profiles were similar Quench has been maintained throughout the
to the prior cycle. Loading Celestia Naphtha run, allowing sustained energy cost
Feed / RG
catalyst increased the bed 3 exo- savings throughout the cycle.
therm from 8°C in the prior cycle
Bed 1 NiMo
to 15°C when processing a similar Case 2: Stretched VGO hydrocracker
feed rate. The higher temperature Bed 2
cycle length and improved product
rise was mitigated by increasing
NiMo
qualities
Jet
quench flow above the catalyst bed Celestia
The second case study focuses on
such that the inlet temperature to Bed 3 another VGO hydrocracker where
Nebula
bed 3 was lowered by 4°C, and the the unit had been previously debot-
reactor outlet temperature increased Bed 4
Celestia
tlenecked to nearly twice the orig-
Diesel
by 4°C. The inter-reactor exchanger Nebula
inal design capacity. The refinery
hot side (total reactor effluent) has a HDC identified a significant opportunity
higher mass flow than the cold side Bed 5
NiMo to extend the cycle length and coor-
(feed only). Increasing the hot side dinate with other units’ shutdown
exchanger inlet temperature by 4°C Bottoms planning, and avoid derating unit
increased the feed side outlet tem- capacity at end of run.
perature by 7°C, and the exchanger Figure 2 VGO hydrocracker reactor Celestia catalyst was loaded in a
duty by 1.7 MW. With Celestia configuration split configuration with Nebula cata-
catalyst loaded, the furnace duty lyst in two catalyst beds in a five-bed
reduces from 16.7 MW to 15 MW, Celestia catalyst’s stability in a VGO hydrocracker pretreat reac-
a net reduction of 10% firing and challenging VGO service has been tor (see Figure 2). The catalyst load
energy consumption. proven to be outstanding, and the replaced a Nebula/NiMo catalyst
load in the prior cycle to achieve a
process objective of stretching the
Reactor dT unit cycle length by 60% and, in
Without Celestia With Celestia
doing so, eliminating a planned full
hydrocracker shutdown and cata-
15F increase in delta T lyst change that would be required
to coordinate with the wider plan
for refinery unit shutdown, equiva-
lent to a 25% reduction in annualised
DEGF

operating expense.
To achieve these goals, a signifi-
cant amount of Celestia catalyst was
needed to boost the overall pretreat
activity by about 130%. Load opti-
misation required detailed kinetic
Normalised feed and process modelling to define
the load plan accurately, and to
Figure 3 VGO hydrocracker reactor exotherm carefully plan the increased tem-
perature rise in the catalyst beds to
achieve multiple process objectives.
Bottoms total nitrogen Without Celestia With Celestia Optimisations and mitigations were
applied in the Celestia catalyst load
design, including increasing the
ascending temperature profile to
achieve product quality and run
length target:
• Balanced the Celestia catalyst and
Nebula catalyst load in two separate
PPM

beds to provide the additional activ-

ity required, and limit the tempera-
ture rise in each bed.
• Lowered the reactor inlet temper-
ature by 12°C, while maintaining
the reactor outlet temperature con-
Normalised feed stant compared to the prior cycle.
• Adjusted the quench gas supply
Figure 4 VGO hydrocracker product nitrogen to manage the reactor temperature

58 Catalysis 2021 www.digitalrefining.com

cat exxon.indd 3 25/02/2021 11:20

 profile and lower the overall reac-
tor weighted average bed temper-
ature (WABT) by 10°C, to meet the Hydrocracker HDN activity Without Celestia With Celestia
target of run length extension (see
Figure 3).
• Set the quench gas supply to the

Normalised HDN WABT deg F

catalyst beds to allow an overall
8.5°C higher temperature rise and
simultaneously matching the inter-
face temperature required into the
hydrocracking catalyst in bed 5.
The key impact of the combined
load of Celestia/Nebula catalysts
was to drive increased aromatic
18F decrease in delta WABT
saturation and lower product nitro-
gen (see Figure 4) at lower reactor
WABT (see Figure 5). The lower Normalised feed
nitrogen slip to the hydrocrack-
ing beds improved cracking cata-
lyst functionality and drove higher Figure 5 VGO hydrocracker normalised WABT
volume swell with a 1 vol% yield
improvement compared to the prior The Celestia/NiMo catalysts load mined to be 25% of bed 4’s volume,
cycle. replaced an all-NiMo catalyst load and 8% of the total active catalyst
The significant reduction in reac- in the previous cycle. The process load. Optimisations and mitigations
tor inlet temperature, while main- incentive achieved by Celestia cat- applied in the catalyst load design
taining similar outlet temperature, alyst included 14% feed rate creep, included the following:
improves the heat integration sys- coupled with feed heavy-up, while • Detailed modelling was com-
tem and results in 5% lower fur- generating improved product qual- pleted to set the maximum Celestia
nace firing energy requirement. This ity and maintaining a cycle length catalyst load that could be accom-
advantage is sustained for most of 2.5 years. A key benefit achieved modated without investment in
of the cycle; capturing the energy was the net lower sulphur in the compression and/or hydraulics.
credit is a critical component in ULSD product, which created a • The feed heavy-up and increased
assessing the opportunity for extra blending opportunity. feed rate led to an overall reduction
value. Celestia catalyst load design was in the reactor start of run exotherm.
Minor modifications to debottle- optimised by detailed process mod- The reactor inlet temperature and
neck the reactor quench gas supply elling to fit within the existing unit’s WABT remained approximately con-
and off-gas purge capacity were capability for heat release manage- stant compared to the prior cycle.
implemented during the unit cat- ment. Celestia catalyst was deter- • Overall quench flow also remained
alyst change; this was required to constant compared to the prior cycle,
manage catalyst temperature con- but the quench gas split was redis-
trol to process quality and cycle tributed with increased quench rates
Quench
length targets. to beds 3 and 4 to counter the higher
Feed / RG heat release generated by Celestia
Case 3: Increased distillate catalyst in bed 4. As a result, the bed
hydrotreater feed rate and NiMo NiMo 4 temperature rise increased by 5°C
improved product qualities compared to the prior cycle, and the
The third case study focuses on a reactor outlet temperature increased
high pressure distillate unit, one of NiMo NiMo
by 6°C compared to the prior cycle
three distillate units in the refinery (see Figure 7).
that supply product to a 10 ppm Celestia catalyst improved the
ULSD combined diesel pool. NiMo NiMo
unit HDS activity (see Figure 8)
Celestia catalyst was loaded in and drove a sharp reduction in die-
stack with NiMo catalyst in bed Celestia sel product sulphur, from 9 ppm
4 of the four-bed high pressure NiMo
NiMo
to 3.5 ppm. The margin impact of
distillate hydrotreater. The unit Celestia catalyst was realised via
operates as two parallel reactors the diesel blend pool, enabling a
processing equal feed rate and Product
more challenged hydroprocessing
quality (see Figure 6). The distil- unit to relax severity and increase
late products from each reactor are run length by operating a higher
combined prior to stabilisation and Figure 6 Celestia catalyst application in a sulphur product into the pool
blending into the site diesel pool. distillate hydrotreater blend.

www.digitalrefining.com Catalysis 2021 59

cat exxon.indd 4 25/02/2021 11:20

 NEBULA® is a registered mark of Albemarle
Bed 4 exotherm comparison and Celestia™ is a trademark of ExxonMobil.
35

30 100% Type II 92% Type II + 8% Celestia Keith Wilson is a consultant with ExxonMobil
Catalyst and Licensing. With 40 years’
25 experience in process engineering, specialising
20 in hydroprocessing and naphtha reforming
DEG C

technologies, he holds a BSc in chemical

15
engineering from the University of Manchester
10 Institute of Science and Technology, UK.
Louis F. Burns III is the Americas Commercial
5
Manager with ExxonMobil’s Catalysts
0 and Licensing group and is responsible for
0 2 4 6 8 10
all technology sales and licensing in the
Cumulative feed to unit per loaded volume
Americas region. With more than 20 years’
Km3 feed ⁄ m3 catalyst
experience in catalyst technology, in research
and development, catalyst development and
Figure 7 Distillate unit exotherm comparison after Celestia catalyst load manufacture, business management, sales and
licensing, he holds BS and MS degrees from
Louisiana State University.
Email: louis.f.burns@exxonmobil.com Dean
Catalyst activity Parker is the Technical Sales Manager for
Downstream Catalysts with ExxonMobil
140 100% Type II 92% Type II : 8% Celestia Catalysts and Licensing. He has 34 years of
experience in the energy industry of which
120
more than 30 years is with ExxonMobil. He
100 has held roles in refinery operations support,
process design, and project teams. He has
80 specialised in hydroprocessing technology
60 for over 21 years and holds a BSc degree in
chemical engineering from Lamar University
40 in the US.
Padmini B Lingaraju is a Market Developer
20
0 2 4 6 8 10 with ExxonMobil Catalysts and Licensing with
Cumulative feed to unit per loaded volume a focus on developing marketing plans and
Km3 feed ⁄ m3 catalyst facilitating technology licensing in the fuels
and lubes area. With more than 10 years’
experience in the energy industry, her previous
Figure 8 Distillate unit activity comparison after Celestia catalyst load roles were in R&D, process engineering, and
technical sales. She holds a master’s degree in
Increasing feed rate with a lower units, shown high catalyst activity, chemical engineering from the University of
reactor exotherm increases the exter- and contributed to improved prof- Cincinnati, Ohio.
nal energy input required. However, itability in 15 applications to date. Pieter Lusse is Senior Technical Advisor for
this was offset by an increased heat The high activity which the catalyst Hydroprocessing Catalysts with Albemarle,
release in the Celestia catalyst bed provides does require a different previously Technical Manager for the Middle
which created an advantage for approach on deployment. The first East and India as well as North and South
America. He graduated in chemical engineering
heat integration, with higher outlet approach is to look at value differ-
from Delft University of Technology, The
temperature offsetting the higher ently. High activity enables multiple
Netherlands.
energy input required to support an benefits to be achieved directly from René Severens is a Technical Advisor with
increased feed rate. the unit, and also from adjacent units Albemarle’s refinery catalysts division and has
The Celestia catalyst’s stability in and blend plant. Secondly, the high worked in R&D, process modelling, process
this service has proven to be out- activity needs to be evaluated for licensing, and in various roles in technical sales
standing. Despite the higher feed safe operation. In most cases, heat and services. He graduated in applied physics
rate and heavier feed, the tempera- release and other issues can be man- from Eindhoven University of Technology, The
ture rise in bed 4 has deactivated at aged effectively at no cost by utilis- Netherlands.
a lower rate and held the delta T for ing different operating practices, and Natasja Berg-Schouten is Business
longer than the all-NiMo load used employing optimal catalyst stacking Manager for Clean Fuels Technologies with
Albemarle. Previously a senior process
in the prior cycle. designs. Case studies presented in
technologist for FCC plant and production
this article demonstrate how Celestia
manager for off-site productions, she
Conclusion catalyst can be applied in three sep- graduated in chemical engineering from the
In five years since its initial com- arate units to yield three very differ- University of Twente, The Netherlands and
mercialisation in November 2015, ent value propositions, each having holds a PhD degree from Eindhoven University
Celestia catalyst has demonstrated a significant impact for the refineries of Technology.
applicability in several types of concerned. Email: Natasja.Schouten@albemarle.com

60 Catalysis 2021 www.digitalrefining.com

cat exxon.indd 5 25/02/2021 11:20

 methane reformer’s furnace flue gas stream
KEN WOHLGESCHAFFEN Chevron Produ

The SCR consisted ofKLAVS BELDRING Umicore

a series of baskets (rectangular
Catalyst switchmodules)
solveswhich
NOxcontained
removal 1.6 mmissues
vanadium-titanium b
Chevron Products Company operated two 1
lobe catalyst
Changing to a corrugated honeycomb pellets
design from a pellet type Figure
(see
ultra-low 1),NOx
NOx burners
for catalytic held
werein placein by
installed one rp
to reduce
reduction of a furnace’s flue gas stream overcame a series of nitric problems
operational oxide emissions from the pla
screens. These baskets are parallel to each other in a
installed in the flue gas duct upstream of the furnace ID
KEN WOHLGESCHAFFEN Chevron Products Company
KLAVS BELDRING Umicore

downstream the ammonia injection grid (see Figure 2).

C
hevron Products Company
operated two 1960s vintage
The SCR co
hydrogen plants at one site. In modules) wh
2000, ultra-low NOx burners were
installed in one plant and a pellet lobe catalys
style selective catalytic reduction
unit (SCR) was installed in the other screens. The
to reduce nitric oxide emissions
from the plants. installed in th
The SCR consisted of a series of
baskets (rectangular shaped mod-
downstream
ules) which contained 1.6 mm
vanadium-titanium based tri-lobe Figure 1 Pellet style catalyst
catalyst pellets (see Figure 1), held Figure 1 Pellet style catalyst
in place by retaining screens. These
baskets are parallel to each other in The catalyst easily achieved the
a grid and installed in the flue gas NOx reduction target. However,
Figure 2 SCR in flue gas duct
duct upstream of the furnace ID fan pressure drop build was a major
and downstream of the ammonia problem over the years. It was
injection grid (see Figure 2). common to see the pressure drop
Ammonia was supplied from increase over time due to particu-
wastewater treatment plants in the lates being collected in the small Figure 2 SCR in flue gas duct
Ammonia was supplied from waste water treatment plants in the refinery (formerly C
refinery (formerly Chevron’s, now holes of the catalyst inlet screens
owned and licensed by Bechtel and in the catalyst pellets in the bas- mental permit requirement for NOx
now owned and licensed by Bechtel Hydrocarbon
Hydrocarbon Technology Solutions, kets. The SCR was acting as a large Technology
Figure Solutions,
2 SCR
reduction. Inc.).
in flue gas duct These
Inc.). These generate anhydrous filter on the furnace flue gas stream, Plant rates were reduced to keep
ammonia from sour water streams. trapping airborne dust, furnace below the maximum pressure drop
anhydrous ammonia from sour water streams. The ammonia is vaporised in an electri
The ammonia is vaporised in an refractory, and rust. Additionally, limit which was set based on the
electric heater, mixed with dilution there was some attrition to the cat- Ammonia
mechanical was supplied
(collapse) fromof waste water tr
strength
mixed with dilution air, and fed to the SCR through the injection grid. The ammoni
air, and fed to the SCR through the alyst due to movement of the pel- the reactor.
now owned Eventually,
and licensed the plant
by Bechtel Hydroc
injection grid. The ammonia flow lets. There was no way to bypass had to be shut down and the pel-
controlled based on the setpoint for NOx exiting the SCR (see Figure 3). The nitrogen o
is controlled based on the setpoint
for NOx exiting the SCR (see Figure
the SCR, and even if we could we
would likely not meet the environ-
let catalyst ammonia
anhydrous removed, screened to water stream
from sour
remove fines, re-installed, and
3). The nitrogen oxides are reduced mixed with dilution air, and fed to the SCR
to elemental nitrogen and water
(steam) across the catalyst according Furnace flue gas
controlled based on the setpoint for NOx exit
to the following reactions: FCV

4 NO + 4 NH3 + O2 = 4 N2 + 6 H2O [1] FT PC

6 NO2 + 8 NH3 = 7 N2 + 12 H2O [2]

Electric SCR reactor
The unit was designed to reduce Anhydrous heating coil
the ~200 ppm NOx (at 3% O2) in ammonia

~700 000 lb/h flue gas by more than

90%. The gas flowed downwards Dilution air Cleaned gas
NOx analyser
and across the catalyst baskets in Blower
this lateral flow reactor (LFR, see
Figure 4). Figure 3 SCR unit layout

www.digitalrefining.com Catalysis 2021 61

cat chevron.indd 1 25/02/2021 11:24

 Catalyst particles
Flue gas Flue gas

Figure 4 Gas flow path through catalyst baskets

Figure 4 Gas flow path through catalyst baskets
topped up with a fresh catalyst. work on the CO2 removal system of
Additionally, the catalyst baskets the plant.
The
were catalyst
hydroblasted easily achieved
to clear the small the NOx reduction target.
Investigation revealedHowever, that pressure drop build was a major
screen holes which tended to plug although we had not done any
problem over the years. It was common to see the pressure drop increase over time due to
(see Figure 5). This was occurring work in the furnace, sufficient
about every 1-3
particulates beingyears outside in
collected loose
of the smallrefractory,
holes of rust,
theand debrisinlet screens and in Permeable
catalyst
wall
the catalyst
planned turnarounds. from full thermal cycling of the fur-
pellets
In 2013in(red thelinebaskets.
in FigureThe 6), weSCRnace was(hotacting
to cold,as then
a large
cold filter
to hotoninstall
the furnace flueupstream
a filter screen gas stream,
of the
had an unusually large increase in again) resulted in a large amount SCR and ‘cold blow’ air through it
trapping airborne dust, furnace refractory and rust. Additionally there was some attrition to the
pressure drop compared with pre- of particulate clogging the SCR. by running the ID fan. This allows
vious years.
catalyst due Thetopressure
movement drop of took the Furthermore,
pellets. There ourwasnormal
no way practice us to collect
to bypass the SCR,and remove particulate
and even if we
a jump upwards following a plant following furnace entry and furnace generated by maintenance work
could
pit stopwe forwould
unplanned likely not meet the
maintenance environmental
maintenance work ispermit requirement
to temporarily forstarting
before NOx reduction.
up the plant. Since
no furnace work had been done,
Plant rates were reduced to keep below the maximum pressure drop limit which was set based
the filtration step was not followed.
on the mechanical (collapse) strength of the reactor. Eventually, the This plant
caused hadthetostep up indown
be shut pres-
sure drop and high rate of pressure
and the pellet catalyst removed, screened to remove fines, re-installed, drop and topped
increase up withthe
following s fresh
2013
turnaround.
catalyst. Additionally, the catalyst baskets were hydroblasted to clear the small screen holes
In 2014, we experienced the high-
which tended to plug (see Figure 5). This was occurring about every est1-3
rateyears
of pressure
outsidedrop
ofbuild
plannedever
seen on the unit (green line in Figure
turnarounds. 6). In less than a year, the pressure
drop was going to hit the high limit.
Our investigation revealed the fol-
lowing causes of the excessive pres-
sure drop:
1) We had Cetek coated the radiant
Figure 5 5 Inlet
Inletscreens
screensbefore
beforeand
andafter cleaning
after cleaning section refractory of the furnace and
re-tubed the furnace, resulting in
In 2013 (red line in Figure 6) we had an unusually large increase
R-305 SCR DP, Normalised in pressure drop compared with lower temperature of the gas enter-
previous16years. The pressure drop took a jump upwards following a plant pit stop for unplanned ing the SCR which caused ammo-
maintenance work on the CO2 removal system of the plant.
nium salt formation
14 2) Large gaps had developed in
Normalised SCR DP, in H2O

Investigation revealed that although we had not done any work in the furnace, sufficient loose
12 the flue gas ducting, drawing cold
refractory, rust and debris from full thermal cycling of the furnace (hot to cold, then cold to hot
ambient air into the gas, cooling it,
10
again) resulted in a large amount of particulate clogging the SCR. Furthermore, our normal
and contributing to salt formation
practice 8following furnace entry and furnace maintenance work is to temporarily install a filter 3) Over-injection of ammonia
screen upstream the SCR and ‘cold blow’ air through it by running the ID fan. This allows us to caused ammonium salt formation.
6
collect and remove particulate generated by maintenance work before starting up the plant. Since We saw the ammonium salts in the
no furnace work had been done, the filtration step was not followed. This caused the step up in catalyst and inlet screens when we
4

pressure2drop and high rate of pressure drop increase following the 2013 turnaround. opened the unit up for inspection
0 100 200 300 400 500 600 700
and confirmed their presence by
Days from SOR
laboratory analysis of samples.
‘10-’11 ‘11-’13 ‘13-’14 1Q14-4Q14 4Q2014-current When we saw this rapid rate of
pressure drop increase in 2014, we
Figure 6 Historical and current SCR pressure drop trends decided to tackle the problem in a

62 Catalysis 2021 www.digitalrefining.com

cat chevron.indd 2 25/02/2021 11:24

 different way. We operate a and dynamic behaviour
Umicore corrugated honey- of ammonia salt inhibition
comb style SCR in another when the new catalyst was
of our hydrogen plants. That designed.
SCR has never experienced We successfully converted
the pressure drop issues the SCR quickly, on time,
we saw with the pellet style and without any safety
catalyst. We decided to con- incidents. We are happy to
vert the pellet style SCR to report that the new catalyst
Umicore’s DNX deNOx cat- is performing very well. A
alyst (see Figure 7). catalyst sample pulled in
We partnered with May 2016 was analysed and
Umicore on a fast-tracked the results were compared
project to replace the SCR in to the initial catalyst design
October 2014. The mechan- to predict the remaining
ical challenge
re 7 Umicore DNX honeycomb style catalyst was to fit Figure 7 Umicore DNX honeycomb style catalyst catalyst life. The slightly
the corrugated honeycomb changed operating condi-
: lhs pic can be cropped
catalyst out)
into the existing ducting catalyst is lowered when ammo- tions were considered and the cat-
with little to no modification of nia salts condense in the micro- alyst life was predicted to be more
the ducting. This required us to pore structure. (In catalyst types than five years (compared to two-
work closely
artnered with Umicore with Umicoreproject
on a fast-tracked on the to with a homogenous
replace the SCR inpore structure,
October 2014.and-a-half-year
The design). This meant
detailed design and installation of the ammonia salts could block the that the plant could skip a catalyst
hanical challengeits was
DNX to modules.
fit the corrugated honeycomb catalyst into
micropore the existing
system, resultingducting with
in replacement since the catalyst was
o no modification ofAnother challenge
the ducting. This was to define
required reduced
us to work overall
closely catalyst on
with Umicore surface projected to be able to provide ade-
the detailed
the catalyst design life because area and consequent lower activ- quate performance until the fol-
n and installationthe
of their DNXchange
catalyst modules. was in-be- lowing turnaround. It is achieving
tween turnarounds, so the first
her challenge was to define the catalyst design life because the catalyst change was target
in- NOx reduction and, more
objective was to make it to the It was important importantly, we have seen negligi-
een turnarounds so nexttheturnaround
first objective wasthe
where to make
cata- it to the next turnaround where the catalyst ble pressure drop increase across
lyst replacements should follow to understand
cements should follow the turnaround schedule for the plant. It was well documented that
this new SCR after almost three
the turnaround schedule for the years of operation (purple line in
plant. Itinwas
onia salts were present thewell documented
existing catalystthat the equilibrium
but it was difficult to quantify the amountFigure and 6). It has clearly been a huge
ammonia salts were present in the improvement over the former pellet
and where it was formed.
existing Normally
catalyst, but itammonia
inhibition levels and
was diffi-salts are identified as being a white sticky style catalyst.
cult to quantify the amount and dynamic behaviour
ance visible around the catalyst, but in this case a greenish substance was also present.
when and where they were formed. Acknowledgements
was identified asNormally,
ammonium chromium
ammonia sulphate
salts are iden- and was mainly found on metal sheets
of ammonia salt We would like to recognise Brian Schlueter

ring the pelletisedtified as being a white, sticky sub- (Project Manager) and Matthew Farrell
catalyst on the inlet side.
stance visible around the catalyst, inhibition when the (Plant Process Engineer) of Chevron who also
contributed to the content of this article.
but in this
ormation of ammonia saltscase a greenish
occurs substancereactions dictated by thermodynamics, so
via chemical
was also present. This was identi- new catalyst was
ging the catalyst fied
to a as
type with an increased porosity should possibly improve performance
ammonium chromium sul-
phate
use the catalyst can and was mainly
accommodate morefound
ammonia
designed
on salts and overall provide a higher activity
Ken Wohlgeschaffen is Team Leader for
the Hydrogen Plants Business Improvement
metal sheets covering the pelletised Network with Chevron Products Company.
densation of ammonia
catalystsalts
on theoccurs while keeping the
inlet side. ity.pressure
However,drop low.
if the Experiences
catalyst has a Hisfromprimary focus is supporting the efficient
The formation of ammonia salts non-uniform pore size distribution,
ore on other units operating at or slightly below the ammonia salt dew point have of hydrogen plants within Chevron’s
operation
occurs via chemical reactions dic- optimal resistance to ammonia salt North American and overseas refineries,
onstrated that the cumulative
tated accessible
by thermodynamics, surface inhibition
so chang- area in the catalyst due
is ensured is lowered
to the when
including operated and non-operated joint
ing the catalyst to a type with an more porous catalyst structure). venture refineries, and leads a team in the
onia salts condenses in the micropore structure. (In catalyst types with a homogenous Downstream pore
increased porosity should possibly Most of the ammonia salts will Manufacturing organisation. He
holds a bachelor of science degree in chemical
ture, the ammonia improve
salts performance
could block because the accumulate
the micropore system, in the inlet catalyst
resulting in reducededge overall
engineering from the University of Calgary.
catalyst can accommodate more where ammonia concentrations
yst surface area ammonia
and consequent salts andlower activity.
overall pro-However, if theAtcatalyst
are higher. the same hastime,
a non-uniform
the
vide a higher activity if conden- ammonia salt dew point is about Klavs Beldring is Global Market Manager
for refinery and chemical applications with
sation of ammonia salts occurs 50°F (28°C) higher in the catalyst
Umicore Denmark. With more than 14 years’
while keeping the pressure drop compared to the bulk phase. The experience in air pollution control technologies,
low. Experiences from Umicore on difference in dew point tempera- he is responsible for worldwide sales and
other units operating at or slightly ture is explained by the effect of the marketing within refineries and chemical
below the ammonia salt dew point capillary forces inside the catalyst, plants, and holds a master’s degree in chemical
have demonstrated that the cumu- so it was important to understand engineering from the Technical university of
lative accessible surface area in the the equilibrium inhibition levels Denmark.

www.digitalrefining.com Catalysis 2021 63

cat chevron.indd 3 25/02/2021 11:24

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