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Q1 2025

REFINING
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 ptqPETROLEUM TECHNOLOGY QUARTERLY
Q1 (Jan, Feb, Mar) 2025
3 Downstream growth beyond 2025

5
Rene Gonzalez

ptq&a

19 Process control and energy management in the 21st century

Jochen Geiger
Ametek Process Instruments

www.digitalrefining.com
25 Mass transfer solutions: Selecting the optimal solution
Mark Knobloch
Merichem Technologies

31 Desalter optimisation strategies: Part 2

Venkatesan Mani
Veolia Water Technologies and Solutions

41 Optimising shell and tube heat exchanger operation

Nicolas Aubin
Petroval

51 Overcoming the complexities of spent caustic treating

Vilas G Gaikar, K V Seshadri and Vaibhav B Kamble
Institute of Chemical Technology

59 Revamping sulphur recovery units with high-level oxygen enrichment

Debopam Chaudhuri, Theresa Flood, Denny Li and Jyoti Bist
Fluor

67 Potential of renewable fuels and SAF

Woody Shiflett
Blue Ridge Consulting

73 FCC unit stripper design and troubleshooting

Warren Letzsch
FCC Consultant

78 Improving energy performance of instrument air system

Subhosree Chakraborty and A Natarajan
Engineers India Limited

83 Corrosion mitigation of amine units using MEA for deep CO2 removal: Part 1
David B Engel, Scott Williams and Cody Ridge
Nexo Solutions

87 Technology In Action
Using CRA barriers to avoid metal degradation in gas plants

Cover
Maximum mass transfer efficiency is achieved using FIBER FILM contacting as it creates a larger interfacial surface
area for treating, minimum mixing energy and enhanced microscopic diffusion to achieve treatment specifications
while minimising any aqueous carryover. Photo courtesy of Merichem Technologies

©2025. The entire content of this publication is protected by copyright. All rights reserved. No part of this publication may be reproduced,
stored in a retrieval system or transmitted in any form or by any means – electronic, mechanical, photocopying, recording or otherwise
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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 responsible for any statements, opinions or views or for any inaccuracies.

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q1 ed com (1).indd 1 11/12/2024 16:49:17

 Make every
molecule matter
At Shell Catalysts & Technologies, we understand how small, unseen chemical reactions
can affect the health of our loved ones, neighbours, and the planet at large. That is
what motivates us in our mission to Make Every Molecule Matter. Every member of
our team is focused on the same goal – developing cleaner energy solutions that
enable industries to tackle global climate challenges starting at the molecular level.
Our experienced scientists and expert engineers collaborate with customers to create
solutions tailored to your specific energy transition and performance challenges. And
when they do, they use the knowledge we gained from Shell’s corporate heritage as the
designer, owner and operator of complex industrial process plants around the world.

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 ptqPETROLEUM TECHNOLOGY QUARTERLY

Vol 30 No 1
Downstream
growth beyond
2025

A
Q1 (Jan, Feb, Mar) 2025
nticipated pro-oil industry support from the new US Administration ensures
fossil fuel-based transportation fuels and petrochemical feedstocks will con-
tinue benefiting the energy industry value chain. Market forces will restart
Editor capital projects put on hold at the onset of the COVID pandemic, including at least
Rene Gonzalez
seven LNG grassroots and expansion projects along the US Gulf Coast.
editor@petroleumtechnology.com
Earlier last summer, Argus projected that three steam cracker projects in North
tel: +1 713 449 5817
America are expected to come online over the next five years, increasing capacity
by 3.6 million tonnes. However, operating rates in all regions are being negatively
Managing Editor
impacted by the combination of high-capacity increases and slower global economic
Rachel Storry
growth. Regardless, the Middle East is experiencing a gas boom.
rachel.storry@emap.com
Saudi Arabia plans to double its gas production capacity by 2030 and has awarded
Editorial Assistant $25 billion in contracts to expand its natural gas production, aiming to increase gas
Lisa Harrison sales by 60% to 2 bcf/day by 2030. Elsewhere, the completion of five refinery proj-
lisa.harrison@emap.com ects in China through to 2028 is focused on the ability to pivot production from fuels
to petrochemicals as market conditions warrant.
Graphics Projects in Africa (such as the 650 kbpd Dangote refinery in Nigeria), India, and
Peter Harper elsewhere will more than compensate for declining refining capacity in mature
economies like Europe. Faced with a dwindling margin outlook, many refiners have
Business Development Director simply opted to close their European refineries and refocus on other regions. The
Paul Mason International Energy Agency (IEA) forecasts a closure risk of 1 to 1.5 million in
sales@petroleumtechnology.com Europe by 2030. However, the growing demand for sustainable aviation fuel (SAF)
tel: +44 7841 699431 may extend a lifeline for some European and US facilities.
A challenge that seems to be affecting every region is a reliable, clean water sup-
Managing Director ply. Besides competing with each other, the refining and petrochemical industry is
Richard Watts competing for water resources with other industries such as steel, power, and data
richard.watts@emap.com centres. While water scarcity has always been a challenge in the Middle East, refin-
ers in Argentina, Brazil, China, the US, and elsewhere are also affected. For example,
Circulation exploitation of Argentina’s vast Vaca Muerta shale play is limited due to the lack of
Fran Havard
fresh water and pipeline infrastructure in that arid basin.
circulation@petroleumtechnology.
Due to high levels of pollution in China’s seven major river systems, refiners there
com
only have as much water availability as Saudi Arabia. Severe drought in many parts of
the US (South Texas, California) leverages planned downstream expansion projects.
EMAP, 10th Floor, Southern House, This has led to a strong emphasis on water and energy conservation, with a focus
Wellesley Grove, Croydon CR0 1XG on thermal systems (preheaters) and mass transfer units (pumparounds, reboilers).
tel +44 208 253 8695 A common thread across all regions is a focus on high-severity FCC units, hydro-
crackers, and increased hydrogen demand. For example, rising hydrocarbon product
Register to receive your regular copy demand in India will result in expanded FCC, hydrocracking, and hydrogen produc-
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fuels consumption will increase from 5.3 million bpd in 2023 to 6.6 million bpd by
2028 while also evaluating pyrolysis oil (pyoil) upgrading to valuable hydrocarbons.
PTQ (Petroleum Technology Quarterly)
(ISSN No: 1632-363X, USPS No: 014-781) However, mixed plastics pyoil upgrading first requires removal of chlorine, silicon,
is published quarterly plus annual Catalysis
edition by EMAP and is distributed in the US
and other impurities. For example, upgraded hydrotreating systems are needed to
by SP/Asendia, 17B South Middlesex Avenue, remove total nitrogen, sulphur, oxygenates, and olefins saturation, but at reduced
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changes to PTQ (Petroleum Technology Plastics Treaty could accelerate these investments. Upgrading pyoil through steam
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from the Publisher at $30 per copy inc postage. is required.
Given that project announcements may reach a critical point in 2025, PTQ will be
ready to share its global access to the best repositories of industry expertise.

Rene Gonzalez

PTQ Q1 2025 3

q1 ed com (1).indd 3 10/12/2024 11:33:00

 Pr o ce ss Not e s

Rethinking Old Problems

More with Less

Projections for global supply and demand of refined Revamp projects are difficult. Limitations imposed by plot
products vary greatly depending on the pace of space, congested pipe racks, and outdated equipment,
technological progress and degree of government to name a few, present unique challenges. Solutions that
policy enforcement associated with reducing rely on excessive margins or comfortable designs lead to
greenhouse gas emissions. Without major advances overspend. Now more than ever, process designers must
in technology, it is hard to imagine a future without find solutions that do more with less.
conventional fossil fuels over the next decade or two.
Based on history, continued rationalization of refining Proven Methods
assets is likely. Small, low-complexity refineries will There is growing awareness that better scope definition
struggle, while large, complex ones will thrive. earlier in the engineering phase saves time, reduces
overall engineering cost, and leads to more successful
Capacity creep through gradual improvement of projects. There is no argument that work completed
refining units will continue to be a differentiating during Conceptual and Feasibility phases is critical to
characteristic for remaining players. Focused revamps getting a project on the right path. Engineers at Process
will play a critical role. Post-pandemic, inflation Consulting Services, Inc. have developed a proven
and a shortage of skilled construction labor have approach that makes the most of this precious time.
dramatically increased costs for refinery revamps. It is
becoming increasingly difficult for many projects to At site, PCS engineers coordinate rigorous test runs, much
meet corporate return on investment thresholds. of it through direct field measurements. Data collected is
invaluable and often leads to low hanging fruit or hidden
gems. Some refinery equipment performs better than
design, and for various reasons others perform worse.
Good test run data allows seasoned engineers to quickly
identify what equipment needs investment and what
equipment can be exploited. This way, solutions are
developed that direct capital expense in the right areas
and overspending is avoided. In one example, pressure
drop measurements of a long crude oil transfer pipe
showed the line could be reused, saving millions of dollars.
Contact us today to learn how PCS’ proven methods can
Field Measurements help you do more with less in your next revamp.

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

More with Less - PTQ 1Q.indd 1 09/12/2024 16:15:16

 ptq&a More answers to these questions can be
found at www.digitalrefining.com/qanda

Q What are the optimal pathways towards increas- naphtha conversion, creating a more streamlined produc-
ing naphtha and LPG production (for petrochemical tion chain.
feedstocks)? Utilising diverse feedstocks is also essential for enhancing
naphtha and LPG yields. Employing a variety of feedstocks,
A Mark Schmalfeld, Global Marketing Manager, mark. including heavier crude fractions and biogenic sources, can
schmalfeld@basf.com, Hernando Salgado, Technical lead to increased overall production. Tailoring processing
Service Manager IMEA, hernando.salgado@basf.com, conditions based on the characteristics of the feedstock can
and Alvin Chen, Global Technology Application Manager, further optimise yields. Additionally, implementing pretreat-
alvin.u.chen@basf.com, BASF Refinery Catalysts ment processes to remove impurities can enhance the qual-
Production of naphtha and liquefied petroleum gas (LPG) ity of the feedstock before it enters conversion units, thus
as petrochemical feedstocks is critical for meeting the improving the efficiency of subsequent processing steps.
demands of various industries. To increase the yield of Effective heat and energy management strategies are a
these valuable products, a multifaceted approach is essen- key consideration for lowering operational costs to make
tial, focusing on optimising processes, catalysts, and opera- the economics of naphtha and LPG production more attrac-
tional parameters. Several optimal pathways can enhance tive. Implementing heat integration and recovery systems
the production of naphtha and LPG via fluid catalytic crack- minimises energy consumption during processing. Efficient
ing (FCC), hydrocracking, and catalytic reforming. energy use not only lowers operational costs but also
FCC is a widely utilised process for converting heavy enhances the economics of naphtha and LPG production.
hydrocarbons into lighter products. The selection of Optimising reactor designs for better thermal management
advanced zeolite-based catalysts is pivotal because they can further improve conversion rates and increase product
can significantly enhance selectivity towards naphtha and yields.
LPG. Innovations in catalyst composition, including the
incorporation of specific metals or alterations to the pore
structure, can lead to improved performance and greater Effective heat and energy
product yields. Additionally, optimising reaction conditions
such as temperature and pressure is crucial for maximising management strategies are a
the production of lighter hydrocarbons. key consideration for lowering
Higher temperatures generally favour LPG yield, while
operational costs to make the
specific pressure adjustments can enhance naphtha pro-
duction. High-severity FCC operation can further maximise economics of naphtha and LPG
light products (LPG, C2=) if the refinery has appropriate production more attractive
product recovery facilities. However, the high coke yield
and high cat-to-oil required to achieve high-severity opera-
tion may require significant feed rate reduction. Hardware Leveraging data analytics can optimise production pro-
design features, such as a dedicated riser to catalytically cesses significantly. Utilising real-time data analytics and
crack recycled naphtha to more light olefins or special riser machine learning algorithms allows for continuous moni-
terminations to increase residence time, are an additional toring and optimisation of production processes. Predictive
handle to maximise light olefins production. maintenance and operational adjustments based on data
Hydrocracking is another critical process that can be insights can enhance overall efficiency. Additionally, devel-
optimised to improve yields. The development of bifunc- oping simulation models can help analyse various scenarios
tional catalysts that combine hydrogenation and crack- and optimise process parameters for maximum naphtha
ing functionalities can enhance the conversion of heavier and LPG production.
feedstocks into lighter products, such as naphtha and LPG. Incorporating sustainability into production processes is
Furthermore, maintaining an adequate supply of hydrogen increasingly important. Exploring carbon capture and utili-
is essential for facilitating hydrocracking, which can further sation technologies can minimise the environmental impact
increase LPG yields from heavier fractions. of increased production, thereby improving the sustain-
Catalytic reforming processes also play a vital role in ability of operations while maintaining high output levels.
converting naphtha into high-octane gasoline components Investigating bio-based feedstocks and waste-to-energy
and generating aromatics. By adjusting catalyst properties technologies can also contribute to naphtha and LPG pro-
and operating conditions, the catalytic reforming process duction, aligning with broader sustainability goals.
can be optimised to maximise LPG yields as a byproduct In conclusion, to optimise the production of naphtha
while simultaneously improving the quality of gasoline and LPG for petrochemical feedstocks, a comprehensive
components. Integrating reforming with other processes approach that encompasses advanced catalyst devel-
can recycle hydrogen and maximise the overall efficiency of opment, process optimisation, feedstock flexibility, and

www.digitalrefining.com PTQ Q1 2025 5

Q&A Q1.indd 5 09/12/2024 16:51:26

 innovative technologies is essential. By leveraging these (USY) zeolite, where they are further converted into naph-
pathways, the petrochemical industry can enhance the tha, LPG, dry gas, and coke. In addition to the FCC catalyst,
yield of these valuable products while improving both specialist additives can be added to enhance LPG yield and
economic and environmental sustainability. The future of increase propylene and butylenes production. Other addi-
naphtha and LPG production lies in the integration of these tives are available that enable operators to boost LPG olefins
strategies to meet the growing demand for petrochemical when FCC gasoline olefinicity is low.
feedstocks in an environmentally responsible manner. Utilising reliable and accurate catalyst and additive addi-
tion systems is essential for optimising the addition of FCC
A Carl Keeley, Head of Key Accounts, Global, Catalyst catalyst and additives. Frequent, small additions are prefer-
Technologies, carl.keeley@matthey.com, Marie Goret- able to infrequent, large ones, as larger additions can upset
Rana, Market Manager Additives, Catalyst Technologies, FCC circulation and catalyst retention, leading to sub-
marie.goret-rana@matthey.com, and Jason Goodson, optimal performance. Likewise, regular, small withdrawals
Regional Sales Manager Additives, Catalyst Technologies, of spent catalyst are recommended. Expertise in the cata-
jason.goodson@matthey.com, Johnson Matthey lyst and additive addition system design is crucial, as poorly
Naphtha is a fraction derived from crude oil and can also designed systems can result in compromised safety and
be obtained from natural gas condensates, petroleum dis- reliability, as well as reduced production of FCC naphtha
tillates, and other less common routes. It is primarily used and LPG.
to produce gasoline and as a feedstock for petrochemical As refining markets continue to evolve, the operational
products. LPG is commonly used for heating and cooking flexibility of FCC units adapts accordingly, enabling refiners
and includes products like propane, butane, and propane- to remain competitive and profitable. The primary product
butane blends. In addition to propane and butane, crude streams consist of naphtha for gasoline production, along
oil refining produces LPG olefins; these olefins are used to with naphtha and propylene for petrochemical production.
enhance gasoline quality and serve as feedstocks for pet- Additional downstream naphtha and LPG olefins process-
rochemical production. ing requires hydrogen and purification steps, requiring
While gasoline demand is projected to decline as the catalyst and absorbents.
US, Europe, and China adopt fuel alternatives and move
towards a net zero economy, demand for naphtha and LPG Q What type of flexibility can be built into a hydrocracker
for petrochemical production is expected to continue to to quickly shift from naphtha to diesel output?
grow (source: bp Energy Outlook 2024).
Crude oil is produced in many locations, with physical A Heather Gilligan, Sr Hydroprocessing Engineer,
properties unique to the location from which it is extracted. heather.gilligan@imubit.com, Imubit
Certain types of crude oil provide a higher yield of straight- Closed-loop artificial intelligence optimisation (AIO) technol-
run naphtha and LPG after distillation. By carefully selecting ogies, such as manipulated available handles (for example,
the crude oil blend to process, oil refineries can maximise reactor temperature and fractionator targets), drive towards
naphtha and LPG production. In addition to crude oil distil- a pre-computed optimal product mix based on a provided
lation, oil refineries can use conversion process technolo- price set. This can occur for a single-unit or multi-unit sys-
gies such as FCC to increase naphtha and LPG production. tem. The AIO model looks at economic objectives and con-
By optimising feedstock selection, equipment, process straints, manipulating the handles to the optimal position to
conditions, catalyst formulations, and additives, the FCC maximise the profit of the unit or the system as a whole.
units can maximise naphtha and LPG yields depending Moving from naphtha mode to diesel mode can have two
on refinery economics. In general, FCC feeds are predomi- transition points. The first is deconverting the tower to maxi-
nantly paraffinic. Paraffinic feeds are easier to crack and mise naphtha into the diesel cut, often to a flash constraint,
normally provide the highest naphtha and LPG yields. once diesel is the more valued product. However, reduc-
Enhancements in feed injection, feed-catalyst mixing, and ing conversion/reactor temperatures to make more diesel
product and catalyst separation can boost naphtha yields. frequently comes with a loss of liquid value gain, so diesel
In addition, routing naphtha to a second reaction zone or needs to have an even greater price advantage over naphtha
dedicated riser can significantly increase LPG yields. before reducing reactor temperatures becomes attractive.
Each FCC unit has its own operating window based on Imubit’s AIO models are built on deep neural networks
its available equipment and other constraints. Generally, that ‘learn’ the nonlinear liquid volume gain and conversion
high operating severity drives both thermal and catalytic curves associated with changing the reactor temperatures.
cracking reactions. However, thermal cracking produces This occurs not just at a single point in time but across the
low-value byproducts like dry gas. Optimising FCC catalyst catalyst cycle as the catalyst deactivates, so the reactor
selection and incorporating additives enables the opera- stays optimised whether this transition occurs with fresh
tor to reduce operating severity and significantly increase catalyst or just before the next changeout.
naphtha and LPG production.
Commercial FCC catalysts are engineered materials to A Peter Nymann, Senior Solution Specialist, Hydro-​
optimise yields within unit constraints. The matrix materials cracking, Clean Fuels, pan@topsoe, Topsoe
perform the precracking of large molecules. The smaller, inter- In general, changes to the operation of a hydrocracker
mediate products produced can then enter the ultra-stable Y should never be made quickly due to safety concerns. It is

6 PTQ Q1 2025 www.digitalrefining.com

Q&A Q1.indd 6 09/12/2024 16:51:26

sulzer.indd 1 09/12/2024 14:45:53
 possible to operate a hydrocracker in ‘swing mode’ where respond effectively to changing product requirements, such
the product objectives switch between maximising middle as shifting from naphtha to diesel output.
distillates (MDs) and maximising naphtha. This requires The design of the catalyst bed is fundamental to the
a margin in the operating temperature of the catalyst, efficiency and longevity of hydrocracking operations. AFS
so it should be a medium-to-high activity hydrocracking technology provides a unique solution by offering high
catalyst. If the unit is operated in recycle mode, maximum available void space and optimised flow channels, mitigat-
(‘max’) MD is favoured, and changing to once-through ing pressure drop, which is critical in maintaining consistent
operation will lead to a switch to a higher naphtha produc- reactor performance. The AFS allows for uniform distribu-
tion rate. tion of reactants, ensuring that the catalyst operates at
High-activity catalyst may be installed in the latter part of peak efficiency throughout its lifecycle.
the hydrocracking reactor, and the temperature profile may Refineries utilising AFS have reported significant
be changed from ‘equal-outlet’ to ‘ascending’ to move more improvements in operational metrics. For instance, one
conversion to the more active catalyst with a higher naph- facility experienced a 150% increase in cycle length com-
tha selectivity. The change in temperature profile may be pared to traditional grading systems, leading to reduced
amplified in case the unit has several reactors, and a heat downtime and enhanced profitability. This extended cycle
exchanger is installed between the two last reactors so life translates to lower operational costs and improved
that the high-activity hydrocracking catalyst can be oper- throughput, allowing refiners to maximise output without
ated colder during max MD production and hotter during compromising product quality.
maximum naphtha production campaigns.
It is important to check that the fractionation section, Hydrocracker flexibility
especially the overhead section and light ends recovery The flexibility built into hydrocracker operations through
sections, can handle higher amounts of light material inad- advanced catalyst systems like AFS and MagAFS is multi-
vertently being produced during maximum naphtha pro- faceted. The ability to quickly adjust operational parameters
duction if the unit normally produces max MD. It should also allows refiners to optimise yields based on real-time market
be checked if the unit is able to provide the necessary lift conditions. When transitioning from naphtha to diesel pro-
of light material during max MD production in case normal duction, the graded bed system can accommodate changes
operation is max naphtha. Hydrocrackers are, in general, in feed composition and processing conditions without
very flexible, and a full range of catalysts from max MD significant downtime. In one case, a refinery successfully
to max naphtha production may be applied with the right shifted its output from naphtha to diesel within a matter of
expertise and safety considerations. hours, thanks to the rapid response capabilities enabled by
the AFS. This adaptability not only meets immediate mar-
A James Esteban, James.Esteban@unicatcatalyst.com, ket demands but also positions the refinery to capitalise on
UNICAT Catalyst Technologies, LLC, Fu-Ming Lee, fmlee@ price fluctuations, enhancing overall profitability.
shinchuang.com, Tzong-Bin Lin, Maw-Tien Lee, Chi-Yao Integration of demetalisation catalysts within the AFS
Chen, Mark Zih-Yao Shen, and Ricky Hsu, Shin Chuang framework enhances the ability to process a wider range
Technology Co., Ltd of feedstocks. By effectively removing contaminants
In the ever-evolving landscape of hydroprocessing, the such as metals, these catalysts prolong the life of the
ability to adapt operations swiftly is paramount for refiners primary hydrocracking catalysts and facilitate smoother
aiming to optimise production and meet market demands. transitions between different product outputs. Facilities
A well-designed graded bed system, particularly utilising employing Unicat’s demetalisation and grading catalysts
Unicat’s Advanced Filtration System (AFS) and MagAFS have reported a minimum of a 30% reduction in catalyst
technologies, is essential for enhancing the operational replacement frequency, significantly lowering maintenance
flexibility of hydrocrackers. These systems not only opti- costs and improving operational efficiency. This reduction
mise catalyst performance but also ensure that refiners can in downtime and/or process unit utilisation is crucial for

XRF analysis showing metals removal by MagAFS filter

Element Metal %, inlet liquid (0.5877)* Metal %, inlet liquid (0.5877)** % Removal by filter
Fe 26.86 wt% 12.67 wt% 98.9
S 9.49 wt% 14.78 wt% 96.2
Mn 843 ppm 0 100.0
Al 0.43 wt% 2.16 wt% 87.6
Cr 0.53 wt% 2.14 wt% 90.0
Mo 224 ppm 0 100.0
Ni 1,529 ppm 1.57 wt% 74.4
Cl 1,337 ppm 1.92 wt% 64.4
Cu 220 ppm 0 100.0
* Total solids in 13 litres of feed liquid to the filter (0.5877g) **Total solids in 13 litres exit liquid from the filter (0.0144g)

Table 1

8 PTQ Q1 2025 www.digitalrefining.com

Q&A Q1.indd 8 09/12/2024 16:51:26

 maintaining continuous production and meeting customer particular propylene, to bridge the gap between refining
demands. and petrochemicals industries.
Significant demetalisation of the feed to the hydro-
cracker using MagAFS is seen in commercial operations Petroriser, FlexEne, and HS-FCC are marks of Axens.
on naphtha (light coal tar). This process has successfully
demonstrated the removal of up to 98% total solids and A Mark Schmalfeld, Global Marketing Manager, mark.
60-100% various metals in the feed steam, as shown in schmalfeld@basf.com, Hernando Salgado, Technical
Table 1. Service Manager IMEA, hernando.salgado@basf.com,
Although vanadium is not shown in the tested liquid BASF Refinery Catalysts
stream, the mass susceptibility (magnetising characteristic) Upgrading the FCC unit can significantly enhance the inte-
of V₂O₃ (1,976 x 10-6 c.g.s. unit) is much higher than that of gration of petrochemical processes within refineries. The
NiO (600 x 10-6 c.g.s. unit). Therefore, V₂O₃ is easier than unit primarily converts heavy petroleum feedstocks into
NiO to be removed by MagAFS. lighter, more valuable products like gasoline and diesel.
In conclusion, the implementation of a well-designed However, by implementing specific upgrades, refineries
graded bed system using AFS and MagAFS technolo- can optimise the FCC unit to produce higher yields of pet-
gies is vital for enhancing the flexibility of hydrocracker rochemical feedstocks, thus improving overall operational
operations. By ensuring optimal catalyst performance and efficiency and profitability.
facilitating quick adjustments in production outputs, these Choosing advanced catalysts that are more selective
systems empower refiners to confidently navigate the com- towards lighter olefins, such as propylene and ethylene,
plexities of the market effectively. The commercial perfor- can significantly increase the output of petrochemical pre-
mance results underscore the tangible benefits of these cursors. Some modern catalysts also have enhanced stabil-
technologies, demonstrating that refiners can achieve lon- ity and longer lifetimes, reducing the frequency of catalyst
ger run lengths, lower pressure drops, and improved profit- replacement and downtime.
ability. As industry continues to evolve, the importance of Modifying the FCC unit’s riser section allows for bet-
such innovative solutions will only grow, positioning refin- ter catalyst distribution and contact time with the feed-
ers to meet both economic and environmental challenges stock. A design that promotes turbulent flow can enhance
head-on. catalyst effectiveness by improving the distribution of
catalyst within the unit. Special bed riser terminations can
Q How can the FCC unit be upgraded to benefit petro- also increase residence time to increase reaction severity.
chemical integration? The implementation of a secondary or dedicated riser to
crack recycled light naphtha also can play a fundamen-
A Francy Barrios, Technology Engineer in FCC and tal role in maximising light olefins yield, especially in the
Sweetening Processes, Axens range of ethylene and propylene under severe reaction
The FCC unit can be upgraded to benefit petrochemical conditions. Additionally, upgrading to advanced catalyst
integration through strategies ranging from some that can injection systems ensures uniform dispersion and optimal
be easily applied to the existing FCC units to modifica- contact between feed and catalyst. Upgrades to injection
tions involving the implementation of new satellite units. systems can also be beneficial when using new advanced
An example of easy and quick implementation could be catalysts.
increasing severity and/or using specific catalyst formula- Adjusting operating conditions such as temperature,
tions and additives (like ZSM-5 zeolite) with high selectivity pressure, and feedstock composition can help in maxi-
to olefins. Other possibilities when evaluating unit modifi- mising desired olefins production. Increasing the sever-
cations to maximise olefins production include: ity of the cracking process can lead to higher yields of
• Incorporation of a separated riser (Petroriser) for light lighter products but requires careful balancing to avoid
naphtha cracking recycling at a higher temperature (oper- excessive coke formation and catalyst deactivation. High-
ating under more severe conditions) than the main riser to temperature equipment such as reactors and advanced
maximise propylene production. separators may need to be changed to handle the desired
• Integration of FlexEne technology, an innovative combi- operational conditions. One particular feature that allows
nation of FCC and oligomerisation technologies, to expand high light olefins yield is the reduction of the hydrocar-
the capabilities of the FCC process towards maximising bons partial pressure by increasing steam streams to the
olefins production. This flexibility is achieved by the oligo- reaction environment. This facilitates the equilibrium con-
merisation of light FCC alkenes (olefins) and recycling ditions to increase the conversion of heavy hydrocarbons
oligomerate for selective cracking in the FCC unit. The to light olefin molecules. In this regard, some units maxi-
FlexEne concept can be easily implemented in existing mising light olefins operate within the range of 10-20%
FCC units. steam-to-feed ratio.
Investment in new FCC technologies, such as HS-FCC Installing high-temperature reactors or modifying exist-
(high severity fluid catalytic cracking) technology, is an ing reactors to handle elevated temperatures safely can
excellent prospect for olefins maximisation. The HS-FCC improve the cracking of heavier feedstocks. Utilising high-
unit is an evolution of the well-known FCC process to reach efficiency separators can better recover lighter products,
a considerably higher level of light olefins production, in minimising the loss of valuable olefins.

www.digitalrefining.com PTQ Q1 2025 9

Q&A Q1.indd 9 30/01/2025 15:34:45

 Petrochemical integration petrochemical production. Investments in new pilot plant
Refineries can install downstream units such as olefin equipment, testing equipment or modifications to existing
conversion units (OCUs), fractionators or propane dehy- designs are often needed to support new R&D innovations.
drogenation (PDH) units that utilise the lighter products By focusing on these upgrade strategies, refineries can-
generated from the FCC. Another interesting integration is not only boost their FCC unit’s efficiency but also enhance
with steam cracking units (SCU) since ethylene produced their capability to produce a broader range of valuable pet-
by FCC can be recovered, while ethane can be further con- rochemical products, aligning with market demands and
verted to ethylene in the SCU. Modifications to piping and economic trends.
the addition of heat exchangers may also be necessary to
connect these units effectively to the existing FCC unit. A Carel Pouwels, Global FCC Specialist Light Olefins,
This integration allows for a more seamless transition from carel.pouwels@ketjen.com, Ketjen
refining to petrochemical production, effectively creating a For petrochemical integration, the maximisation of light
more versatile and adaptable processing facility. olefins by the FCC unit is essential. Within a given unit con-
Coprocessing biofeedstocks or lighter hydrocarbons figuration, the first choice is to enhance process conditions
alongside conventional feeds in the FCC unit can diversify that maximise unit severity. Maximising reactor outlet tem-
the product slate. This method not only helps in meeting reg- perature is one of the first independent process variables
ulatory requirements for renewable content but also allows to consider; preferably, the temperature is enhanced to
for the production of unique petrochemical intermediates. the range of 545-550°C. More extreme process conditions
Alternative feeds often require dedicated storage systems. can be applied when the FCC unit is upgraded to so-called
Additional equipment modifications could include enhancing ‘high-severity’ FCC units, whereby reactor temperatures up
feedstock pretreatment systems to accommodate biofeed- to 600°C are possible.
stocks or lighter hydrocarbons. This might involve upgrading Depending on the metallurgy, a revamp might be needed.
pumps and heat exchangers to handle different viscosities Due to the increased dry gas and LPG production, the refin-
ery needs to address the wet gas compressor handling too. If
not yet present in the current downstream configuration, the
Coprocessing biofeedstocks or refinery needs to expand with deC2, deC3, and deC4 recovery
units while also building a C₃ splitter to make chemical-grade
lighter hydrocarbons alongside propylene.
conventional feeds in the FCC unit Next to the enhanced severity by a higher reactor tem-
can diversify the product slate perature, conversion can also be enhanced by increased
catalytic cracking reactions through more catalyst circula-
tion (or cat-to-oil ratio). Consequently, more gasoline mol-
and properties of the new feedstocks. Additionally, FCC ecules are generated, which can be cracked to light olefins.
licensors have unique equipment modifications they can Note, however, that hydrogen transfer reactions will also
recommend for co-processing, particularly around how the increase and can negatively impact C3=/LPG. The key to a
alternative feedstocks are injected into the FCC. high olefins yield is control of the various competing reac-
Implementing advanced process control systems can tions. Hence, the reduction of hydrocarbon partial pressure
optimise the FCC unit’s performance in real-time. These through enhanced dispersion and lift steam is also of impor-
systems can adjust parameters dynamically based on feed- tance. This way, light olefins are preserved, and reactions
stock variations and desired product specifications, maxi- to paraffins by unwanted hydrogen transfer are minimised.
mising yield and minimising waste. Many advance control While dedicated unit hardware and process conditions
systems are already available today in most refiners, such as for high-severity operations are needed, the third element
real-time monitoring tools and automated control systems. of importance is the FCC catalyst that is optimised for such
This includes the installation of advanced sensors for tem- application. While every FCC unit with its specific feed is
perature, pressure, and composition analysis to enable real- unique, it thus requires a unique catalyst solution, prefer-
time adjustments and optimisation of the cracking process. ably from a repository of expertise with a wealth of industrial
experience in high-severity FCC applications, ranging from
Upgrades the lightest to the heaviest feedstocks. With decades of sup-
Advanced distributed control systems (DCS) upgrades can ply to various FCC units of all licensors, Ketjen’s max propyl-
dynamically adjust operational parameters based on feed- ene catalysts AFX and Denali AFX with optional usage of its
stock characteristics and desired product yields, while upgrad- DuraZOOM-MA additive, have achieved record olefins yields.
ing heat exchangers and integrating heat recovery systems Ketjen’s new ZSM-5 investment at its Bayport site will sup-
can improve FCC unit energy efficiency. By capturing and port the industry in this move to petrochemical integration.
reusing heat generated during the cracking process, refiner-
ies can reduce overall energy consumption and enhance the A Fu-Ming Lee, Principal Author, fmlee@shinchuang.
economic viability of producing petrochemical products. com, Shin Chuang Technology Co., Ltd, James Esteban,
Continuous investment in R&D can lead to the discov- Sr Technical Manager, James.Esteban@unicatcatalyst.
ery of new catalysts, processes, and technologies that can com, Unicat Catalyst Technologies, LLC
further enhance FCC performance and its integration with To further upgrade the FCC unit for enhanced petrochemical

10 PTQ Q1 2025 www.digitalrefining.com

Q&A Q1.indd 10 10/12/2024 17:18:42

 A long history of looking

AHEAD

For nearly a century, Grace catalysts have kept fuel and petrochemical
feedstocks flowing from the industry’s largest refineries to the trucks,
trains, planes, and ships that keep our world running.

We are leveraging our long history of innovation in fluid catalytic cracking

to develop products that enable lower carbon fuels and help meet the
challenges of the energy transition.

grace.com

GRACE.indd 1 09/12/2024 15:11:47

 Original slurry oil (SO-O) Treated slurry oil (SO-1)
80
20

2
.1

.9
64

16

5
.3
60

2
.6

15
14
15

7
.8
6
.3
40

10
%

10
10

49

93
7.

6.
20

35
53
5.

97
5

4.

3.
15

81
14
48

37
96

79

85
27
69
5.
42

79
05
52
67
34

46
40

04

3.
4.
3.

3.
2.

2.

1.
2.
1.
1.

0.
1.
1.
0.
0.

1.
0.

0
0.

28

02
0.

0.
0
.4
.1
15
.1
.6
.5
.7
17 .5
19 .4
22 .8
25 .7
29 .5
.3
39 09
44 .5
51 .1
.3
00
11
13

17
19
22
25
29
29
80
68
98
76

04
72
22
34

60

7
10

.4

.1
15

.1
.6

.5

.7

.5

.8

.7

.3
7.

8.

11

13

17
19

22

25

29

33

38

44
nm(10 -9m) nm(10 -9m)
Duplicate treated slurry oil (SO-1A)
*From similar particle size distribution (PSD) of SO-1 and
SO-1A, it confirmed only particle sizes smaller than 44.3 nm
6
.3

15 were left in the slurry oil after filtered by UMF filter.

14
9

9
.6

.4
12

12
3
.2
10

10
58
8.

47
45
00

70

7.
7.
%

7.

6.
61

44

5
4.

4.

97
2.

83

15
0.

03
0.

0.

0
6
6

7
10

.4

.1
15

.1
.6
.5

.7
.5

.8

.7

.3
6.
7.

8.

11

13

17
19
22

25
29

33

38

44

nm(10 -9m)

Figure 1 Particle size distribution (PSD) of original and treated slurry oil

integration, refiners can leverage a variety of advanced alone generated 5 million tons of SO annually. Therefore,
catalysts and technologies, including Magnetic Advanced the potential benefits of upgrading SO for petrochemical
Filtration System (MagAFS) and drop-in FCC catalyst addi- and fuel applications are substantial.
tive solutions. The following case summary focuses on a Small catalyst fines, mostly smaller than 20 µm (10-
technology aimed at slurry oil (SO) upgrading. SO is one of 6m), in SO are extremely difficult to remove. Conventional
the major FCC unit products, but with low quality and very methods, such as gravity sedimentation, centrifugal sepa-
limited applications, mainly due to its significant content of ration, filtration, and electrostatic precipitation, are inef-
small catalyst fines (3,000-6,000 µg/g). fective for fines removal, especially nanometer size (nm,
Worldwide SO production from FCC units is huge in quan- 10-9m) particles. The development of an effective process
tity. For example, even 25 years ago, FCC units in China for removing catalyst fines from SO to upgrade its qual-
ity to transportation fuels and improved petrochemical
Typical compositions of the tested SO applications is not only profitable but also environmentally
preferred.
Slurry oil source Daqing Aramco MagAFS technology has been developed to remove par-
Density, g/ml 0.9690 1.0162 ticles larger than 50 nm. The tests were conducted in a lab
Carbon residual, % 4.95 7.27 UMF unit consisting of two magnetic filtration chambers
Refractory index 1.5433 1.5797 connected in series. Typical compositions of the tested SO
Relative molecular weight 365 316
are listed in Table 2.
SO was fed through the lab unit at a controlled flow
C, wt% 87.92 88.11
rate. Treated SO samples at the exit of the first and sec-
H, wt% 10.72 9.41
ond chambers were collected for particle size distribu-
S, wt% 0.33 1.66
tion (PSD) analysis. Samples of solid particles removed
N, wt% <0.3 0.48
by the first and second chambers were also collected for
H/C 1.4528 1.2816
Ni, ppm 1.8 8.4
PSD analysis. Focusing on the nm size particles, PSD of
V, ppm 0.1 2.6
the original SO (SO-O), treated SO (SO-1), and duplicate
treated SO (SO-1A) are given in Figure 1. It shows that
Saturates, % 53.3 26.7 with original SO (SO-O), more than 64% of the solid par-
Aromatics, % 41.9 67.0 ticles were larger than 6,000 nm (or 6 µm). Only particles
Resin, % 4.1 4.9 smaller than 44.3 nm were left in treated SO (SO-1). The
Asphaltenes 0.7 1.4 result was confirmed by PSD in the duplicate treated SO
(SO-1A).
Table 2 Further details of the operation are revealed in Figure

12 PTQ Q1 2025 www.digitalrefining.com

Q&A Q1.indd 12 09/12/2024 16:51:27

 PSD of SO treated in 1st chamber PSD of SO treated in 2nd chamber

5
.5
20 20

19

3
.2
0
.6
17
16
15 15

8
1

.3
.3

12
5
8
12

7
.0
.9

.9
11
10

10
10 0 10

67
%

43
9.

63

8.
8.
68

7.
51

31
37
6.
6.
50

6.
5.
5.

21

86
5 5

4.

17
89

82
3.
05

3.
2.

96

2.
41

2.
1.

82

. .45
32

1.

36
10

04
0.
.5 0.

0.
2 .. 0
.8 0.
.7 0.
0 0
8
6
6
7
10
.4
.1
15
.1
.6
.5
.7

00

7
10

.4

.1
15

.1

.6

.5

.7

.5

.8

.7

.3

.7
5.
6.
7.
8.

8.
11
13

17
19
22
25
29
33
38

11

13

17

19

22

25

29

33

38

44

50
60
51
nm(10 -9m) nm(10 -9m)

PSD of solids removed in 1st chamber PSD of solids removed in 2nd chamber
80 40

7
.3
1

33
.3
63
60 30

40 20
%

5
.1
6

.0
.7
12

11
10
2

20 10
.9

41
9

14
.0

7.
86
11

42

46
30

62

4.
51
64
91

3.

3.

50
64
6.

19
11

66

75
2.
36

2.
2.
2.

1.
1.

1.
1.

0.

0.
0.

0 0
.5

.3

09

.5

.1

.3

00

10 3
11 .8
13 .9
15 .2
17 .9
19 .4
22 .8
25 .7
29 .5
.3
09

44 .5
51 .1
.3
00
76

7.
98

76

04

72

22

04
59
18
09
29
80
68
98
76

04
72
22
34

60

34

60
87
25

29

39

44

51

39
nm(10 -9m) nm(10 -9m)

Figure 2 PSD of solids removed in first and second UMF chambers/slurry oil exiting first and second UMF chambers

2, where SO exiting the first chamber contained mainly on-site testing by installing a small portable MagAFS unit
6-500 nm particles, but still had 20% 6,000+ nm par- through a slip-stream connection without disruption to
ticles. SO exiting second chamber contained only 9-44 normal FCC unit operations.
nm particles (no 6,000+ nm particles). Most larger par-
ticles (2,600-6,000+ nm [63.3%]) were removed by the Q What FCC and hydrotreater modifications are needed
first chamber. Smaller particles (800-6,000+ nm [33.4%]) to increase refinery coprocessing of renewable feedstocks?
were removed by the second chamber. Figure 3 compares
the PSD of the original (SO-O), treated (SO-1), and dupli- A Francy Barrios, Technology Engineer in FCC and
cate treated (SO-1A) slurry oil, based on the analysis of all Sweetening Processes, Axens
samples collected from the experiments. Renewable feeds available for co-processing in FCC units
The result confirmed that any solid particles having present different properties and impurities compared to
a size larger than 50 nm (44.3 nm) were successfully conventional feedstock, impacting operation, heat bal-
removed from the slurry oil by MagAFS process technol- ance, catalyst activity, and unit performance. This impact
ogy. It is also possible to provide low-cost and convenient will even depend on the co-processing ratio. The main

80

Original Treated Duplicate treated

60 SO-O SO-1 SO-1A

40
%

20

0
6

10

.4

.1

15

.1

.6

.5

.7

.5

.8

.7

.3

.4

.8

.7

.5

09

00
6.

7.

8.

6.

4.

2.

2.
11

13

17

19

22

25

29

33

38

44

29

80

68

98

34

60
7

2
17

19

22

25

29

39

44

51

nm(10 -9m)

Figure 3 Comparison of PSD of original and treated slurry oil

www.digitalrefining.com PTQ Q1 2025 13

Q&A Q1.indd 13 30/01/2025 15:35:11

 modifications that can be required in FCC units to increase Relevance: Lighter renewable feedstocks may require
the co-processing of renewable feedstock are dedicated different flow dynamics compared to heavier petroleum
feed injection nozzles, bio-oil storage and feed lines, and feedstocks.
equipment materials upgrading.
Dedicated feed injection nozzles, specifically for injecting Feed injection
fast pyrolysis bio-oil into the FCC riser, ensure refiners can Modification: Install dedicated feed nozzles for renewable
co-process bio-oils while minimising potential plugging or feedstocks.
corrosion due to mixtures of fossil and renewable feeds Relevance: Renewable feedstocks may not be stable at
that might result in blending issues. The latter is due to the typical FCC feed conditions and may have to be handled
presence of many oxygen-containing molecules that result differently (thermal stability, fouling, solution compatibility)
in a polar phase immiscible with fossil feedstock. to ensure reliable operation.
Bio-oil storage and feed lines should be built with mate-
rial resistant to corrosion over long-duration exposure Operating conditions adjustment
to bio-oils feeds. For renewable feedstock, organic acid Modification: Adjust temperature and pressure settings to
(RCOOH, which is measured by total acid number [TAN]) optimise the processing of renewable feeds.
and chlorides are the main impurities that could cause cor- Relevance: Each type of feedstock may have an optimal
rosion issues. The long-chain organic acids usually pres- temperature and pressure range for effective cracking. For
ent in these feedstock are weak acids that slightly acidify example, animal fats typically require slightly different con-
free water in contact with the feedstock, such as in storage ditions than vegetable oils.
systems.
Equipment materials upgrading of the reaction sec- Downstream hardware modifications
tion and main fractionation overhead section should be Modification: Increase sour water handling capacity.
evaluated due to corrosion risks associated with chloride- Relevance: Processing high concentrations of renewables
containing compounds. Against this backdrop, the Axens (particularly bio-derived oils) can produce significant water,
technological solutions provide support in co-processing CO, and CO₂ yields in the riser.
matters, offering feedstock characterisation, pilot plant
tests, catalyst evaluation, and corrosion and revamp stud- Hydrotreater modifications
ies to deal with the co-processing challenges related to the Hydrogen supply and management
incorporation of renewable feedstock in commercial units. Modification: Upgrade hydrogen supply systems to ensure
consistent and adequate hydrogen availability for the
A Mark Schmalfeld, Global Marketing Manager, mark. hydroprocessing of renewable feeds.
schmalfeld@basf.com, Hernando Salgado, Technical Relevance: Many renewable feedstocks have higher oxy-
Service Manager IMEA, hernando.salgado@basf.com, and gen content and thus require more hydrogen for effective
Alvin Chen, Ph.D., Global Technology Application Manager, hydrotreatment.
alvin.u.chen@basf.com, BASF Refinery Catalysts
To increase the coprocessing of renewable feedstocks in Catalyst adaptation
FCC units and hydrotreaters, specific modifications are Modification: Utilise catalysts that are optimised for renew-
necessary to enhance compatibility, efficiency, and yield. able feedstocks, particularly those that can effectively
Each modification must be tailored to the type of alter- remove oxygen and sulphur.
native feedstock being processed, such as vegetable oils, Relevance: Different feeds, like palm oil vs used cooking oil,
animal fats, or other bio-based materials. The following may require unique catalyst properties to achieve desired
discussion focuses on suggested modifications, their rel- saturation and hydrodesulphurisation outcomes.
evance to various feedstocks, and recommended pretreat-
ment changes. Reactor configuration
Modification: Modify existing reactors to accommodate
FCC modifications higher flow rates and pressures, which can enhance the
Catalyst selection processing of lighter biofeedstocks.
Modification: Use catalysts specifically designed for renew- Relevance: Different feedstocks can have varying viscosi-
able feedstocks, such as those that are more effective in ties; heavier oils might necessitate different reactor designs
cracking triglycerides found in vegetable oils. compared to lighter, more fluid alternatives.
Relevance: Different feedstocks have varying molecular
structures. For instance, vegetable oils require catalysts Pretreatment modifications
that promote the cracking of larger hydrocarbon chains into De-oxygenation
lighter fractions. Modification: Implement de-oxygenation processes such
as hydrotreatment or thermal treatment before feeding into
Reactor design enhancements the FCC, hydrotreater, or downstream equipment.
Modification: Implement dual riser reactors or modify exist- Relevance: Reducing oxygen content can enhance yield
ing risers to allow for better mixing and residence time for and performance by minimising the formation of undesir-
alternative feeds. able byproducts during processing.

14 PTQ Q1 2025 www.digitalrefining.com

Q&A Q1.indd 14 09/12/2024 16:51:27

 Filtration and degumming and feedstock properties, renewable feedstocks for copro-
Modification: Install filtration systems to remove impurities cessing can be summarised in two categories.
and solids from feedstocks like vegetable oils. The first category is fats, oils, and greases (FOG), which
Relevance: Impurities can lead to catalyst poisoning and are triglycerides from edible oils, non-edible oils, used
operational issues. For instance, the presence of phospho- cooking oil (UCO), and animal fats. The second category is
lipids in crude vegetable oils can hinder catalytic activity. bio-oil derived from either pyrolysis or hydrothermal lique-
faction of agricultural, forestry, municipal wastes, and other
Heating and viscosity reduction lignocellulosic materials.
Modification: Preheat feedstocks to reduce viscosity and Common to both FOG and bio-oil is the potential for high
improve flow characteristics. levels of various contaminants, particularly alkali and alka-
Relevance: Heavier feedstocks, like used cooking oils, may line earth metals, phosphorous, chlorine, and silica. High
benefit from preheating to allow for better mixing and levels of metals can create corrosion concerns and impact
improved processing in the FCC or hydrotreater. catalyst activity and lifetime. The most difficult of the FOG
group to treat would be UCO with elevated chlorides, acid-
Mixing and emulsification ity, metals, and other contaminates.
Modification: Use emulsification techniques to create a Crude FOGs are the next most challenging, with elevated
homogenous mixture for coprocessing. metals and contaminates. UCO, crude FOGs, and bio-oils
Relevance: Certain feedstocks may not blend well with will exhibit elevated contaminant metals and chlorides
conventional feeds without emulsification, leading to incon- with attendant corrosion concerns that may require lining
sistent processing and lower yields. storage tanks and selection of corrosion-resistant metals
for process equipment and piping. These materials are not
These modifications are integral for optimising the copro- commonly processed at this time. They are not compatible
cessing of renewable feedstocks in FCC and hydrotreaters. with fossil fuels and have stability concerns. They will have
Each type of alternative feedstock may require specific extremely high water (~20 wt%) and oxygen (~20 wt%)
adaptations in both equipment and processing conditions levels with extremely high metals and impurities. Since they
to maximise yield and performance. By implementing these do not compete with food, they are considered substan-
changes, refineries can better integrate renewable feed- tially more desirable as a renewable feedstock.
stocks into their existing processes, thereby enhancing Since bio-oils are far less commonly used, this response
sustainability while maintaining economic viability. will focus primarily on the FOG effect on hardware changes/
additions.
A Darrell Rainer, Global FCC VGO Specialist, darrel.
rainer@ketjen.com, Jon Strohm, R&D advisor, james. FCC unit
strohm@ketjen.com, Cliff Avery, Global FCC Process Shipping/receiving and storage: Typically, feedstocks are
Advisor, cliff.avery@ketjen, Ketjen delivered by ship or truck and should be diverted to a sepa-
Modifications necessary to enable renewable feedstock inte- rate storage tank. Time-dependent feed quality degrada-
gration within existing operations are dependent primarily on tion is a greater concern for FOGs and bio-oils relative to
the differences in feed properties compared to conventional conventional feedstocks (a storage life of three months is
petroleum feedstocks. Renewable feedstock properties usually considered acceptable, depending on ambient tem-
related to increased and new contaminant levels, thermal perature and specific feedstock characteristics). Ageing of
stability and reactivity, and high oxygen content are gener- FOGs can result in increased fatty acid content, leading to
ally the main factors influencing operational, process, and higher acidity and corrosion concerns, while ageing of bio-
equipment modifications. Based on chemical composition oils can result in gumming and fouling of process vessels

Renewable source Main hydrocarbon types Characteristics

FOG Edible and non-edible oils Natural oils and fats, virgin or Known and predictable
Used cooking oil (UCO) processed: Tryglycerides and composition
Animal fats (tallow) fatty acids Some impurities present:
Flue gas
Na, K, Si, P

Renewable source Main hydrocarbon types Characteristics

Bio-oils Agricultural wastes Products from pyrolysis or Not compatible with fossil
Steam
Forestry wastes hydrothermal liquefaction: fuels and stability concerns
Municipal wastes Unsaturated compounds No competition with food
Other lignocellulosic but also high oxygenates High impurities present:
materials O, alkalis, Ca, Fe, Mg, P, Cl
Steam
Air
Common catalytic requirements to successfully process these feeds:
Catalyst technologies with high accessibility and materials resistance
Steam Feed Control of deoxygenation pathways to minimise impact on product slate and FCC unit operations

Figure 1 Overview of FCC unit renewable coprocessing feed options

www.digitalrefining.com PTQ Q1 2025 15

Q&A Q1.indd 15 09/12/2024 16:51:27

 WG Amine
Corrosion in OVHD due to HCN and Dryer C2
treater
NH4Cl formation – nitrogen & halides
LSO
Reactor Sponge Various
effluent SW abs. fractionation C2
WG units C3=
∆PC
TC
RSO nC4
SW iC4
Flue gas
LC Primary C4
HCN abs.
LCN
Feed impact on product slate
Catalyst performance LCO Gaso.
Deoxygenation pathways
splitter
Metals tolerance ∆PC
Steam
HCO
HCN
Debutaniser
Steam Debutaniser
Steam Emulsion and foaming (amine carryover) in downstream
MCB gas treatment
Air ∆PC
Acid / base reactions
pH impact on scrubbers
Possible further reaction of light oxygenates (gums and acids)
Steam Feed Light oxygenates in gas separations

Injection and stability of bio-oils Corrosion issues

Free-water expansion Metals/halide contaminants
Storage

Figure 2 FCC coprocessing – process and catalyst challenges

and piping and potential phase separation due to high smoke point of the FOG. Elevated temperatures above the
water content. smoke point can result in elevated total acid number (TAN),
It is recommended that this feedstock be sent to an isolated increasing corrosion concerns and dehydration reactions
feed nozzle. The licensor should be consulted regarding the and resulting in biogenic carbon losses as gums and car-
need for any special modifications to the existing nozzle or bon deposits in feed lines, heat exchangers, and injectors.
the introduction of entirely new designs (see Figure 1). Considerations must be made for any process component
When considering bio-oils, a specially designed nozzle in contact with these high-TAN renewable feedstocks, with
is necessary due to the high water content and miscibil- improved corrosion-resistant properties where required.
ity issues. The feed nozzle design and operation should One of the main objectives for coprocessing is to incorporate
account for the water-to-steam volume expansion and low biogenic carbon into fuels to maximise biogenic hydrocar-
temperature mixing with the dispersion steam. Bio-oils bon products; switching to a catalyst system that maximises
have poor thermal stability due to the high oxygen content, hydrodeoxygenation would be preferred. However, maxi-
particularly of pyrolytic sugars present in the oils. Removing mising hydrodeoxygenation results in lowering the H/C ratio
of the final product slate and results in higher coke and lower
product value. To minimise the impact on the product slate
One of the main objectives for and/or improve overall hydrocarbon yields, catalysts favour-
ing decarboxylation will result in maximising deoxygenation
coprocessing is to incorporate while maintaining higher H/C ratios of the final products at
biogenic carbon into fuels to the expense of lower biogenic carbon in the final hydrocar-
maximise biogenic hydrocarbon bon product compared to hydrodeoxygenation. Dehydration
and decarbonylation will result in increased biogenic carbon
products rejection as coke and CO (see Figure 3).
In the product recovery section, changes in the water and
process/chemical chemistry are necessary. The increased
water through thermal pretreatment is not feasible due to chlorides, CO and CO₂, oxygen-containing hydrocarbons,
hydrolysis and decomposition of the pyrolytic sugars at and lower pH will result in increased corrosion, emulsion,
temperatures above approximately 50°C. Decomposition and foaming in the downstream units. This negative impact
of sugars present results in severe coking and gumming of must be addressed in cooperation with the water process
process lines, heat exchangers, and feed nozzles. Without chemical provider.
pretreatment operations for the stabilisation of the bio-oils
by removing these sugars, the bio-oil will require separate HPC
feed nozzles to directly inject bio-oil into the FCC riser while When introducing renewable feedstocks to the hydrotreater,
minimising any preheating (see Figure 2). there are several factors to consider that might require
FOG feeds are particularly susceptible to thermal degra- some hardware modifications. First of all, the H₂ availability
dation at typical FCC preheat conditions, which is above the must be evaluated: biofeed processing requires additional

16 PTQ Q1 2025 www.digitalrefining.com

Q&A Q1.indd 16 09/12/2024 16:51:28

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 Thermal/acid catalised water removal
Dehydration Partial deoxygenation results in
Biogenic coke formation
High coke and low
Water + coke (biogenic) aldehyde and ketone formation biogenic carbon recovery
Reduces H/C ratio of products

Oxygen rejection as CO and H2O Rejects biogenic carbon and

Decarbonylation Reduces H/C ratio of products hydrogen from system
Water + CO (biogenic) O Coke formation
Higher slurry and coke production
R + CO + H2O from bio-oil and conventional feed
HO R

Oxygen rejection as H2O Highest biogenic carbon retention

Hydrodeoxygenation Hydrogen donation from conventional feeds in products Max biogenic
Water + coke (oil) O
Increased coke from conventional carbon recovery
R + 2H2O feeds
HO R

Oxygen removal as CO2 Minimises hydrogen loss from

products with minimal coke
Decarboxylation Retains H/C ratio of products
CO2 (biogenic) O Max products
Biogenic carbon rejection as CO2
R + CO2
HO R

Minimise products with minimal impact on product slate?

The Inherent Conflict: OR Maximise biogenic carbon in products?

Figure 3 Major deoxygenation pathways influencing coprocessing of oxygenated feeds

H₂ consumption, so the first limitation to increase the bio- are being applied across all process and operational areas
feed intake is set by the MUG compressor capacity. in many different business applications. Some have been
The second operational aspect to evaluate is the maximum in place for many years, such as machine learning to find
delta T allowed. This is generally set by the reactor design. anomalies in the operation of rotating equipment as part of
However, this limit can be managed up to a certain extent predictive maintenance. However, it was only recently that
(by recycling the product and diluting the feed, for example). AI and machine learning strategies moved from an advisory
Additional flexibility is also provided by the quench, with capacity to closed loop, where an action is automatically
more impact on subsequent beds than the top bed but also executed as a result of the AI model calculation.
on overall T profile. There are also some hardware limita- In this newer world of closed-loop AI optimisation,
tions that might require revamp and modifications. The first Imubit is seeing refiners capture the highest value when
one is related to the high acidity of the biofeed that can lead applying the technology to complex and nonlinear pro-
to corrosion problems upstream and within the reactor. In cesses. Some notable applications include conversion units,
general, there are some minor preventative actions available such as FCCs and hydrocrackers, and multi-unit feed and
to mitigate this (such as pretreatment of the biofeed and N₂ multi-unit product optimisation. One example of the latter
blanketing in the biofeed tank). In more severe cases, chang- involves balancing T90s across multiple units to push the
ing metallurgy upstream might be the only option. A second diesel pool to the T90 limit and upgrade molecules from
hardware limitation can be the formation of salt downstream gasoil.
caused by the presence of Cl in the biofeed. In this case, wash Some of the quantified benefits that have been reported
water injection can be applied to mitigate this complication. publicly by customers using closed-loop AI optimisation
The last aspect to consider is the formation of certain include:
byproducts upon biofeed coprocessing. It is recommended • 0.5°F improvement in average ULSD T90 vs baseline
to confirm that the high-pressure separator has sufficient (reported by Delek US at 2024 AFPM Summit)
capacity to deal with the amounts of propane and water • 2% FCC debutaniser tower throughput capacity increase,
formed. On the gas-make side, a series of components will removing bottleneck and allowing them to push FCC con-
be formed (methane, CO, and CO₂) that will impact the recy- version (reported by Big West Oil in June 2024 Imubit
cle gas purity. For this reason, it is recommended to increase webinar)
the purge rate compared to a conventional operation. • FCC liquid volume yield improvement of 0.6% (reported
by Big West Oil in June 2024 Imubit webinar).
Q What process and operational areas have refiners • Reduced conservatism in diesel flash target by 2°F,
demonstrated a positive ROI in the application of artificial enabling increased, on-spec, diesel throughput (reported
intelligence and machine learning strategies? by Big West Oil in June 2024 Imubit webinar).
• 25% reduction in sub-optimal coke drum cycles sig-
A Heather Gilligan, Senior Hydroprocessing Engineer, nificantly reducing coker giveaway (reported by Marathon
heather.gilligan@imubit.com, Imubit Petroleum Corporation Garyville Refinery at AFPM Summit
Artificial intelligence (AI) and machine learning strategies 2024).

www.digitalrefining.com PTQ Q1 2025 17

Q&A Q1.indd 17 09/12/2024 16:51:28

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Q3_EUROTECHNICA.indd 1 05/06/2024 14:54:23

 Process control and energy
management in the 21st century
Key online measurements and technologies for safe and optimal refinery operation,
highlighting potential energy savings that can lead to reduced CO2 emissions

Jochen Geiger
AMETEK Process Instruments

R
efinery working conditions are changing due to the concentrations are changing, it is necessary to measure the
increasing processing of sour crude oil as the avail- sulphur concentration in the crude oil itself. Not only is the
ability of sweet crude diminishes. As a result, refiners incoming crude oil sulphur concentration different, but the
require more flexibility because, in addition to environmental viscosity of the crude will also alter, resulting in a change to
impact monitoring, sulphur dioxide (SO₂) emissions have the final product’s viscosity.
to be reduced without expending more energy (as this can When measuring the percentage level of sulphur in crude
increase overall CO₂ emissions). All of this brings significant oil, the viscosity of the stream being introduced to the pro-
challenges to the operators of a refinery. cess gas analyser is one of the primary hurdles to overcome.
Behind the scenes, there is a growing focus on analyser In many cases, the fluid only remains liquid at temperatures
solutions and the next generation of process instrumenta- >150°C, which is a challenging temperature for many com-
tion, which will be reviewed with a specific emphasis on plex process gas analysers. Therefore, selecting the appro-
multicomponent/multisensor technologies and their corre- priate measurement solution is a critical consideration. Most
sponding process control improvements. existing online instruments are based on X-ray or ultraviolet
The foundation of this methodology is a holistic perspec- (UV) fluorescence, which are analytical methods designed
tive on analyser design. Rather than adhering to one-size- for low- and mid-level sulphur measurements in lighter sam-
fits-all solutions, analysers are tailored to each application. ple streams.
This careful customisation enhances accuracy and efficiency, For crude oil, heavy vacuum gasoil (VGO), residuals, or
ensuring a seamless fit. heavy bunker fuel, it has long been common practice to
Along with this holistic approach is the integration of tai- use instruments based on a radioactive detector technique.
lored sampling systems. Aligning analysers with sampling However, this has become increasingly difficult to select
systems will mitigate potential complexities in sample condi- and implement, as it presents the system designers and end
tioning systems. Streamlining workflows and boosting oper- users with significant safety factors and complicated certifi-
ational fluidity, strategic technology selection is a hallmark of cation processes. An alternative method is X-ray transmis-
this methodology (see Figure 1). sion, which offers the benefit of no permanent radioactive
source, eliminating many of the safety concerns and certifi-
Measuring high sulphur-containing crude samples cation issues.
The supply of crude oil is becoming more challenging in In addition, the entire measuring system is suitable for
several geographic regions. Crude compositions can change heavy fuels, as it can be maintained at temperatures up to
due to supply methods, which may shift from pipelines with 250°C. Almost no filtration is required to protect the meas-
a stable composition to ocean vessels with variable com- uring system from potential impurities in the stream. All
positions, requiring more refinery flexibility. In addition, it is this makes the blending control simpler, with lower mainte-
essential to monitor the environmental impact and reduce nance requirements. Bunker fuel measurements occur quite
emissions to comply with regulatory requirements. far downstream in the refinery but have recently become
Maximum and minimum sulphur concentrations can vary more important as part of the global effort to reduce harm-
between 1% and 6%. Not only are the chemical, catalytic, ful emissions from points of use. Sulphur in bunker fuel can
and thermal reactions within refineries dependent on stable eventually be oxidised into SO₂ when burned and must be
crude oil, but piping specifications must also be considered reduced.
regarding the maximum permitted sulphur concentration. For a long period, bunker fuel was an extremely heavy fuel
For example, if a refinery is designed to operate at a sulphur that only became a flowing liquid at high temperature and
level of 3-4% and the incoming crude is at 5.5%, a modified was expected to have high levels of sulphur. Since 2020, the
blending control system will be required. International Marine Fuel Specification (ISO 8217:2024) has
For many refineries, sulphur level measurements in the limited the sulphur concentration of marine bunker fuel to
parts per million (ppm) range are an important part of the 0.5% (the previous limit was 4.5%). As a result, more accu-
final product quality control system. When feedstock sulphur rate and controlled blending is required.

www.digitalrefining.com PTQ Q1 2025 19

Ametek - Copy.indd 19 09/12/2024 16:56:42

 Amine treating Refinery fuel E
Fuel gas
Claus sulphur plant Sulphur
Other gases LPG H2S
Gas processing Merox treaters
Butanes
Gas
Gas H2 Gas H2 H2S from sour water stripper
Light
Hydrotreater Isomerisation
Naphtha plant Isomerate
Gas H2
B
Gas H2
Atmospheric distillation

Heavy naphtha
A Hydrotreater Reformate
Catalytic
Jet fuel reformer
Crude oil Merox treater Jet fuel and/

Gasoline blending pool

Gas H2
Kerosene or kerosene Hydrocracked gasoline

Hydrocracker
Gas H2
Diesel oil
Hydrotreater Diesel oil

Atmospheric Diesel oil

Heavy vacuum
gas oil gas oil Gas
Evacuated i-butane
Alkylate
non-condensibles Gas H2 Alkylation
Atmospheric FCC feed Gas Butenes, pentenes
Light
bottoms vacuum hydrotreater Gas H2
FCC gasoline

Fluid catalytic
cracker (FCC)
gas oil Hydrotreater
Vacuum Naphtha
distillation Heavy
vacuum A FCC gas oil
C Fuel oil
gas oil Gas
Vacuum residuum Coker naphtha
Delayed coker

(after hydrotreating and reforming)

Coker gas oil H2S to sulphur plant
Asphalt
blowing Asphalt
Air Sour waters

steam stripper
Sour water
Petroleum coke
Finished products are shown in blue
Sour waters are derived from various distillation tower CO2
reflux drums in the refinery Natural gas Hydrogen Steam
The ‘other gases’ entering the gas processing unit H2
Steam synthesis
includes all the gas streams from the various process Stripped water
units
D

Figure 1 List of measurement points

Another critical measurement point is the FCC inlet, Moisture and corrosion
where heavy and light VGO is obtained. For optimal FCC The measurement of moisture in gases is one of the more
operation, it is essential to control the amount of incoming complex and difficult applications found in industrial pro-
sulphur to stay within design specifications. Measuring sul- cesses. Moisture, or water traces in combination with other
phur at the outlet of the FCC unit provides assurance that components, can easily become a very corrosive mixture, such
operations are as intended or helps identify an issue that as moisture in CO₂ or together with H₂S, affecting stationary
has developed and should be addressed. sections of process equipment such as pipes, reactors, and
Process analyser solution options for sulphur contami- vessels. Another important factor is that water traces can
nants include X-ray transmission measurements). These are negatively influence process yields. Water concentrations may
not the only methods for monitoring sulphur, SO2, and/or lead to line freezing due to cold weather and other factors.
H₂S measurements in refineries, gas plants, chemical pro- Moisture measurement is different due to the fact that
duction environments, and even steel mills and coke plants. every analyser, especially process analysers, needs to be
UV and infrared (IR) technologies are also used to measure verified and calibrated. The reading of the instrument can
these undesired byproducts along production pathways, in be higher than the concentration expected by the pro-
the final product, and at emission points. Many plant oper- cess engineer. The protocol with every other gas analyser
ational systems are designed based on an expected range is to connect a bottle with a certified calibration gas to the
of sulphur components and can quickly be damaged or instrument, verify the reading to be correct, or see that an
become inefficient if those ranges are exceeded. adjustment is needed. However, this cannot be done with a
Purchasing contracts limit the amount of sulphur compo- moisture analyser.
nents that may be present in the purchased products, and Water concentration in the cal (calibrated) gas bottle will
variances can require additional processing or even create vary depending on the pressure and temperature of the bot-
purchasing disputes. Finally, the release of H₂S and SO₂ are tle. It is possible only under laboratory conditions to have a
both highly regulated emissions. H₂S is extremely toxic and proven water concentration in a background of nitrogen (N₂)
lethal to humans, and SO₂ is known to contribute to acid or methane (CH₄). The given concentration in a cal gas bottle
rain development. Measurements of the amount of each is only valid at a very limited pressure window and only true
of these compounds are required to ensure that emissions and certified at one temperature. That makes the use of such
stay below specific limits. a bottle in the field impossible.

20 PTQ Q1 2025 www.digitalrefining.com

Ametek - Copy.indd 20 09/12/2024 16:56:43

 Water
vapour
Combustibles CO2 emissions Hydrogen (H2)
Carbon
losses NOx emissions Nitrogen
monoxide
Fuel usage (CO)
Typical O2
only operating Combustion
Excess inefficiencies due
set point fuel Useful heat transfer reduced to unburned fuel
(combustibles)

No excess O2
in flue gas
300 ppm Air
Extremely high
200 ppm combustibles
100 ppm Δ
CH4 + 1.6O2 + N2 0.6CO2 + 1.6H2O + 0.4CO + 0.4H2 + N2
0% 1% 2% 3% 4%
Excess O2 15,500 BTU/Lb. = 35% less efficient (HEAT LOSS)

Figure 2 Optimum combustion set point Figure 3 Air-to-fuel ratio reaction

When measuring moisture of other gas mixtures, only that CO measurement is not equal to COe measurement. A
quartz crystal microbalance (QCM) non-equilibrium analys- final point for consideration involves a case of ‘flame lost’,
ers have an internal calibration standard known as a moisture which is a sudden loss of flame, meaning ongoing fuel sup-
generator. These generators make use of the fact that most ply to the combustion chamber. An explosion can occur if
materials have a fixed specific permeation rate. The most undetected. This can be simply detected with one more sen-
common devices use a Teflon tube as the permeation device. sor to measure CH₄.
The permeation rate will not change (no ageing effects)
as long as the temperature and the flow to the device are Instruments for clean energy projects
constant. This permeation can work from the outside (with Carbon reduction clean energy processes are increasing with
the tube in a water bath) or inside (with the tube filled with the need for carbon capture. The most common projects
water). For accuracy of the device, flow through and temper- involve H₂-generating units. The three key technologies for
ature stability are essential. producing H₂ are:
Undetected higher moisture concentration can cause • SMR: Steam methane reforming units
pipeline/process equipment corrosion, line plugging due to • ATR: Auto thermal reforming
freezing (ice formation), and lower process yield and/or lower • SGP/POx: Shell gas partial oxidation/partial oxidation.
product qualities. In any of these cases, the cost of such an In order to call hydrogen (H2) blue, carbon capture must be
event can be quite high and, in the case of corrosion, cause implemented. There are several components to be measured
irreversible damage. to monitor process reliability and maintain close process
control. The requirement here is for multicomponent/multist-
Process heater optimisation ream and flexible instrumentation. The right combination
One of the most common operating units in a refinery or any needs to be defined. As with all previously discussed points,
chemical processing plant is the process heater, used to force the ‘golden rule’ of sample system engineering applies: know
chemical reactions, combust products, or generate energy or your process conditions; invoice the right people; simplify the
steam. When deciding what to optimise on such a device, in system; and select the right equipment.
today’s world we need to ensure that we optimise energy
consumption as much as possible. This is typically achieved SRU process optimisation
by controlling the combustion set point. Two control param- The following tail gas treating unit (TGTU) discussion is an
eters are important: one is the oxygen (O₂), and the other is amine-based TGTU within the sulphur recovery unit (SRU).
the carbon monoxide (CO) concentration. Too much O₂ will The purpose of the TGTU is to convert all remaining sulphur
result in heat losses and, therefore, less efficiency. If O2 is too components carried over from the modified Claus unit into
low, the CO can be too high, which translates into ‘unburned’ H₂S. This happens in the catalytic section of the TGTU pro-
fuel – a direct loss of energy. Figure 2 illustrates this function. cess. The reduction reactor utilises a cobalt-molybdenum
A CO measurement is sufficient to optimise combustion, catalyst (also mentioned as CoMo bed). The CoMo catalysed
but this does not take into consideration the safety aspect of reactions are shown as follows:
any combustion process. In any combustion process, there SO₂ + 3H₂ g H₂S + 2H₂O
could be ‘unburned’ combustibles left, which may potentially S + H₂ g H₂S
create an explosive mixture. No combustibles displayed as H₂O + CO g H₂ + CO₂
CO equivalent (COe) are detected by any direct CO sensor COS + H₂ g CO₂ + H₂S
systems. Instead, a catalytic sensor is required for this kind CS₂ + 2H₂O g CO₂ + 2H₂S
of measurement. Figure 3 shows an extreme example, but The first step of the reaction does require H₂, which can be
it is unlikely. present as a byproduct of the modified Claus reaction and
Measuring COe is becoming more of a must when dis- also generated by an inline reduction burner or provided from
cussing H₂ fired heaters. It is, therefore, important to note an external source. Regardless of the H2 source, to ensure

www.digitalrefining.com PTQ Q1 2025 21

Ametek - Copy.indd 21 09/12/2024 16:56:43

 Stack gas
emissions monitoring AT7
SO2, NOx (mass flow)

Quench column
off-gas H2
AT5 AT6
Cobalt Absorber outlet
Quench column H2, H2S plus COS & CS2
molybdenum pH meter
reduction
reactor ATx
Thermal oxidiser
Absorber &
stripper
columns
H2S
H2S recycle COS
AT4 Quench to Claus inlet CS2
column
Reduction reactor
off-gas
low SOx H2

Figure 4 TGTU with sample points

that the ‘sulphur compounds to H₂S’ reaction is complete, the availability of multicomponent instruments, additional
an excess of H₂ is required after the reduction reactor. In the measurements became interesting.
second step, the H₂S needs to get separated and returned to Knowing the importance of excess H2 in the TGTU and
the inlet of the modified Claus reaction furnace. This step is recognising that an additional measured component does
based on an amine absorber/regenerator system. not add significant cost to an analyser, a redundant H₂ meas-
The overall sulphur recovery efficiency (modified Claus urement should be added at this point. By adding the H₂
reaction and TGTU) is required and predicted to be at 99.9+%. measurement, redundancy can be achieved without signif-
This is confirmed by measuring the total mass emission of icant extra cost. The same can be said about adding a COS
SO₂ at the exhaust of the final thermal reactor or ‘stack’. and/or CS₂ measurement; both can be used to determine the
Sample point description details include (see Figure 4): condition of the CoMo bed catalyst. If the COS and CS₂ val-
• AT4: At the reduction reactor outlet, there is always an ues are increasing, the CoMo catalyst needs to be replaced
uncertainty of SO₂ slip. We know that according to the or another operational variable such as flow rate or temper-
manufacturer’s specification for a new, fresh catalyst, the ature needs to be adjusted, or the modified Claus unit has
SO₂ concentration should be below 10 ppmv and not more some operational concern that needs to be addressed.
than 100 ppmv for a used, aged catalyst. We need to keep in When looking into the combination of the two previously
mind that under all circumstances, SO₂ breakthrough into the described sample points, redundant H₂ measurement will
amine absorber must be avoided. Driven by new instrument ensure optimal performance of the TGTU. It should reduce the
developments, this measurement can now be considered as cost of replacing contaminated amine and minimise downtime.
feasible as a direct measurement. If H₂S is measured at the quench tower outlet and absorber
• ATx: Quench tower water pH measurements to prove that outlet, it will be possible to measure and control absorber effi-
no SO₂ is entering and changing the water into ‘sour’. ciency online on a 24/7 basis. Process control of the amine
• AT5 and AT6: Quench tower and absorber tower outlet recycling/regeneration is possible based on the H₂S IN and
measurements and control. OUT measurement. The final quality control parameter is the
• AT5: Quench tower outlet measurement H₂ and H₂S. SO₂ mass emission to be measured at the thermal oxidiser
Since the TGTU process was first introduced as the Shell outlet. Only mass emissions can tell the true sulphur recovery
Claus Off-Gas Treating or SCOT Process, H2 measurement rate. Knowing the H₂S entering the process and the amount of
has been expected at this point and included in the original SO₂ leaving the oxidiser will provide an accurate value.
system design. The purpose of measuring H2, as previously
mentioned, is to ensure that excess H₂ is coming out of the Summary
CoMo reactor. H₂S is also measured at this point so that Beyond technological novelty, the focus remains on practical
operators and the automated control system understand the and tangible benefits. This ensures innovative solutions not
amount of H₂S entering the absorber. Sample gas measure- only meet theoretical expectations but also enhance real-world
ments at this stage of the process are easier to handle vs performance. From application-specific analyser designs to
AT4 measurement at the quench tower inlet because of the tailored sampling systems and strategic technology choices,
lower temperature of the process gas. Any particulates will this holistic approach propels SRU operations towards opti-
also have been removed in the quench tower. mal efficiency. Knowledge, understanding, and awareness
AT6 absorber outlet H₂ and H₂S and COS/CS₂: The pri- training are essential to maintaining the instruments, enabling
mary measurement at this point was defined as a single the achievement of required optimisation targets.
H₂S measurement to ensure the performance of the amine Jochen Geiger is Business Development Manager at AMETEK Process
absorber. By gaining knowledge about the application and Instruments. Email: jochen.geiger@ametek.com

22 PTQ Q1 2025 www.digitalrefining.com

Ametek - Copy.indd 22 09/12/2024 16:56:43

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ENDRESS HAUSER.indd 1 09/12/2024 14:37:04

 Mass transfer solutions: Selecting
the optimal solution
Utilising low differential pressure, high surface area mass transfer devices reduce
treating unit size while meeting more stringent regulations and improving performance

Mark Knobloch
Merichem Technologies

I
t is extraordinary to find a chemical process that does Mass transfer market
not require either a preliminary purification of raw mate- Research firm Market Research reported late last year that
rials or a final separation of products from byproducts. the mass transfer market is expected to grow substantially
In the oil and gas industry, hydrogen sulphide (H2S) and over the next few years. It attributes this to an increas-
other mercaptans present in crudes must be removed from ing demand for purified substances in various industries,
intermediate or final products for performance, economic, including petrochemicals and refining, where there is a
environmental, and health reasons. The goal is to find the need to separate and purify crude and gas. The analyst
best way to do this, and, in many cases, mass transfer is the firm also calls out aggressive research and development for
root of the solution. efficient and cost-effective distillation systems along with
innovative techniques that are expected to revolutionise
Mass transfer the mass transfer industry. Continuously evolving regula-
There is a library full of technical literature on commer- tions and standards related to the use of environmentally
cial processes used for impurity removal. However, it has friendly and energy-efficient distillation systems on federal
become clear that not all treatments are equal, and not all and state levels are also driving market growth.
treatment offerings using mass transfer as the solution can
be counted on to work the same way. Technology solution
Selecting the optimum treatment for removing impurities There is a highly adaptable, non-dispersive mass transfer
from hydrocarbon streams has been a challenging task device that utilises caustic, amine, and other aqueous solu-
for industries around the world. Conventional dispersion tions as the treating reagent to remove acid gases, mer-
and phase separation methods are subject to numerous captan compounds, and other aqueous-soluble impurities
shortcomings. The conventional method of contacting two from liquid and gas hydrocarbon streams. It consists of a
immiscible liquids is to disperse one liquid thoroughly into vertical cylinder packed with thousands of metallic fibres,
the other as small droplets. Where small droplets are gen- also known as a ‘fibre bundle’. The hydrocarbon needing
erated using high differential pressure mix valves, larger treatment and the aqueous treating solution are both intro-
droplets are formed using trays. Impurities pass between duced to the top of the bundle and flow cocurrently through
the two phases at the surface of the droplet. the bundle (see Figure 1).
Even when the dispersion-based system provides ade- As both phases flow down the bundle, the aqueous
quate treatment, separating the two phases is usually phase adheres to, or wets, the metal fibres and is continu-
extremely inefficient. The smaller the droplet size, the more ally renewed as it flows down the length of the fibre via a
separation time is required. Since the separation drum has combination of gravity and interfacial drag between the two
a fixed volume, increasing the quantity of smaller, micron- immiscible phases. The hydrocarbon phase flows through
sized droplets to improve mass transfer results in insuffi- the cylinder concurrently and between the aqueous-wet-
cient time to separate fully. Thus, the micro-droplets ‘carry ted fibres. The large surface area and tight packing of the
over’ with the treated hydrocarbon phase, causing minor to metal fibres bring ultra-thin falling films of the aqueous
moderate contamination in downstream equipment. If the phase into intimate contact with the hydrocarbon phase.
shear force is set too high across the mixing device to force The interfacial surface area produced is orders of magni-
more mass transfer, stable emulsions can form, resulting in tude larger than in conventional droplet dispersion devices,
massive carryover out of the separator vessel. allowing impurities to diffuse easily between phases.
Mass transfer can only be improved by creating more After the mass transfer is completed, both phases enter
numerous and smaller droplets to increase the surface a separator, which quickly allows complete phase separa-
area. This is more effectively accomplished using non-dis- tion using their density difference. Due to the lack of micro
persive hydrocarbon treating processes for caustic, amine, droplets, bulk separation takes only a few minutes.
and acid. This technology has many benefits. Its large interfacial

www.digitalrefining.com PTQ Q1 2025 25

Merichem.indd 25 09/12/2024 17:02:21

 Untreated hydrocarbon PC

Treated hydrocarbon

FC FC

Thiolex Thiolex
LC LC

Hydrocarbon
Caustic FC
M

H2S removal: H2S + 2NaOH Na2S + 2H2O Fresh caustic

CO2 removal: CO2 + 2NaOH Na2CO3 + H2O
Mercaptan extraction: RSH + NaOH RSNa + H2O Sulphidic caustic

Figure 1 Thiolex unit configuration

surface area, microscopic diffusion distance, and continu- numerous shortcomings, including lack of turndown capa-
ous renewal of the aqueous phase combine to yield mass bility, plugging, flooding, channelling, unpredictable treat-
transfer efficiencies far greater than possible with conven- ing results, long settling times, aqueous phase carryover,
tional dispersive treatments. Since it is highly customisable, generation of dilute aqueous wastes, lower service factor,
fibre bundle geometry allows the treatment of a wide range hydrocarbon losses, larger plot space, product contam-
of hydrocarbon types with different physical properties. ination, and additional processing steps and equipment
The inherent low differential pressure drop across the fibre needed to separate phases.
bundle and the fast phase separation time facilitate the ret- Even when the dispersion-based system provides ade-
rofit of this treatment process into existing systems as a quate treatment, separating the two phases can be prob-
debottlenecking solution. lematic. The mixture must remain in the phase separator
The cocurrent flow is more forgiving during hydrocar- until the caustic droplets settle out by gravity, which can
bon flow upsets, allowing treatment even under sub- take hours. As the treating requirement becomes more
optimal conditions. Carryover is virtually eliminated due to stringent, mixing energy is increased to maximise interfa-
the avoidance of droplet formation as the aqueous phase cial surface area. This results in a greater dispersion of the
adheres to the fibres in the contactor rather than being aqueous phase, requiring exponentially longer separation
dispersed into the hydrocarbon phase. Emulsion formation times.
is also effectively eliminated. Since efficient phase contact Stable emulsions can form in the mixing device, result-
occurs without dispersion, stable emulsions rarely form in ing in massive carryover from the separator vessel. Due to
the unit. excessive carryover, expensive equipment such as knockout
Similarly, the system does not depend on gravity settling vessels, sand filters, and water wash units must be installed
for micro droplets or emulsion coalescence, which greatly downstream to remove the dispersed aqueous phase from
reduces separation time. Processing vessels can be much the treated product. Treatment is often interrupted if an
smaller. In most cases, expensive downstream coalescers emulsion develops. Excessive emulsion formation can dam-
and other clean-up equipment are not required. However, age downstream equipment and foul separators and other
coalescers can further enhance the separation, taking the mass transfer equipment.
ultimate separation down to almost non-detectable levels
of carryover of aqueous treating liquids in the hydrocarbon Treating processes
product. The smaller size separation requirement translates Merichem Technologies’ proprietary Fiber Film Contactors
to less expensive equipment cost, and with fewer pieces of create a process for caustic extraction of mercaptans, naph-
smaller equipment, plant space is more efficiently utilised. thenic acids, and H2S impurities from hydrocarbon streams.
Most importantly, this method of mass transfer achieves This mass transfer device creates an interfacial surface
maximum removal of impurities from the hydrocarbon to between hydrocarbon and caustic phases in a non-disper-
meet today’s stringent standards as set forth by the US sive manner. It consists of a multitude of thin fibres packed
Environmental Protection Agency’s Clean Air Act. in a cylindrical column, where the hydrocarbon and aque-
ous phases flow cocurrently downward, forming a thin film
Challenges of other solutions on the fibre surface.
Conventional caustic treating processes with dispersive This eliminates problems associated with the principle
mixing devices and phase separation were once the only of droplet formation and dispersion of one phase into the
option available to the industry. However, conventional other, which are often encountered in conventional sul-
dispersion and phase separation methods are subject to phur extraction/sweetening units. The fibre pack creates

26 PTQ Q1 2025 www.digitalrefining.com

Merichem.indd 26 09/12/2024 17:02:21

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 a good system for distribution of liquids mercaptan as sulphur. The feed contained
in the whole cross-section of the device, a C1/C2/C3 mix of mercaptans, and the
avoiding channelling problems that might treated product stream had to contain less
Hydrocarbon
be associated with random packings or than 100 wtppm total sulphur. The treated
structured packings without intermediate NGL streams had to each contain less than
re-distribution. 16 wtppm mixed mercaptans and pass a
Fresh caustic
Optimal treating systems are custom- maximum 1 rating on the copper strip test.
designed to meet refiner requirements, Shortly after the new unit start-up,
then engineered and fabricated to the Merichem was asked to revise the initial
customer’s specifications, whether the process design information based on new
need is for a completely new facility or design basis information the operator dis-
Fibre
a minimal retrofit to upgrade existing covered. Working collaboratively with the
equipment. operator through the COVID-19 pandemic
This technology offers a unique design period, several relatively minor changes
with a significantly larger interfacial sur- were identified in the unit infrastructure,
face area, using minimum mixing energy. resulting in the implementation of some
It allows for enhanced microscopic dif- minor equipment upgrades.
fusion and a continuous renewal of the Following these changes, a minimum
aqueous phase. Mass transfer efficiency 33% increase in design nameplate capac-
is improved by an order of magnitude, ity was successfully demonstrated. The
which reduces operating costs. The liq- next challenge was to improve product
uid surface area is significantly increased, purity coming from the Merichem process,
which improves the efficiency of the pro- given the changes in feed characteristics.
cess and allows for higher flow rates with Working in the same manner, changes
little to no emulsification, carryover, or to improve recycled caustic quality were
high-pressure drop during phase transfer. Figure 2 Fiber Film mass transfer identified, thus increasing the efficiency of
Pressure drop through this mass transfer device the mass transfer in the Thiolex process,
device is low and on par with pressure which produced a cleaner product at the
drop experienced in traditional random and structured higher throughput rates.
packing implementations. Due to the flexibility of Fiber Film as a mass transfer
This mass transfer device has low fouling characteristics device, there was no requirement for internal modifica-
in most hydrocarbon/caustic treating systems and can nor- tions to any vessel or system. An available hydrocarbon
mally be restored to clean condition by simple water wash- solvent was introduced into the caustic regeneration pro-
ing. There are no moving parts in the Merichem device, cess, which increased the removal of oxidised sulphur com-
and in most cases the fibre-packed bundle can be easily pounds and oils from the circulating caustic. The end result
removed from the service vessel for cleaning or replace- was less sulphur in the hydrocarbon product stream and
ment. The robust design of the equipment allows this mass reduced sulphur removal load on downstream equipment,
transfer device to extend its life through several turna- even with design impurity changes.
rounds with proper care and regular cleaning.  At a client site in central Louisiana, Merichem identified
In the proprietary FFC Plus Contactors, Merichem com- issues with mercaptan sulphur removal from their liquefied
bines the Fiber Film Contactor with a typical coalescing petroleum gas (LPG) stream. The operator was using a fixed
element directly to further enhance the separation of the solid bed of caustic to treat the LPG, and mass transfer was
hydrocarbon and liquid treating layers. This results in very limited. Frequent changeout of the solid bed was costly and
low to no carryover of the aqueous phase in the hydrocar- messy to manage. Merichem designed a system capable of
bon product. This improved mass transfer and separation treating a stream of saturated LPG containing 566 wtppm
can lead to a significant capacity increase and improvement of H2S and 500 wtppm of mercaptans as sulphur.
in impurity removal. The treated product specification was set to contain nil
H2S, less than 10 wtppm total sulphur, pass the copper
Results from case examples strip corrosion test at 1A, and contain less than 1 wtppm
Selecting the optimum treatment for removing impurities of caustic entrainment measured as Na+. The bed of solid
from hydrocarbon streams is a challenging task for any cus- caustic pellets was replaced with a single-stage Thiolex
tomer. By providing the means to offer a series of proven caustic wash system to improve mass transfer and reduce
liquid hydrocarbon treating technologies, companies can caustic entrainment in the downstream product, with the
offer services that complement their own technology port- added benefit of reducing chemical use and frequent main-
folios. Examples include: tenance requirements.
 For an operator in Western Canada, Merichem The same end user in Louisiana was also treating a ker-
Technologies (formerly Merichem Company) originally osene stream for the production of jet fuel for the aviation
designed Thiolex/Regen technologies to treat a natural gas industry. Jet fuel has many stringent specifications, not
liquid (NGL) stream containing more than 900 wtppm of the least of which is appearance. The presence of alkaline

28 PTQ Q1 2025 www.digitalrefining.com

Merichem.indd 28 09/12/2024 17:02:21

 water in the final jet fuel product may cause the kerosene
to have a ‘hazy’ appearance. The typical specification for
jet fuel appearance is ‘clear and bright’. The solution was
to offer a new transfer device FFC Plus, which worked by
combining the advantages of Fiber Film Contactor with tra-
ditional woven coalescer elements.
An additional advantage of this equipment is that it can
be installed in the same separation equipment without
modification, where there was previously a traditional Fiber

All from
Film Contactor and possibly a downstream coalescing ele-
ment. The difference was immediately apparent following
start-up of the new equipment. The treating unit was pro-

one Source!
ducing on-specification kerosene with sufficient sulphur
compound removal, and the appearance of the final jet fuel
product was now clear and bright. Not only was the cus-
tomer able to produce saleable product, but the recycle of
off-specification material was significantly reduced.

Fast Delivery
Solutions exist for mass transfer Worldwide
treating that meet the ever-
changing needs of refiners and Duranit®
others to satisfy the tightening Catalyst Support
Material
regulations on the fuels market
Support Plates /
Grids
Conclusion
Mass transfer is a game-changer in client processes such
Droplet Separators /
as gas absorption, desorption, distillation, and extraction,
Demisters
among others. Technological innovation and advancements
have optimised the performance of mass transfer equip-
Feed Devices:
ment, making it more widely used in many processing and
treating applications. These devices have been successfully Gas / Liquids
used in many applications of liquid/liquid and gas/liquid
extraction. Liquid distributors /
In utilising low differential pressure, high surface area Collectors
mass transfer devices instead of legacy high differential
pressure shear devices, the size of treating units is reduced, Random Packings
operations and performance are greatly improved, and - Ceramic
more stringent requirements are easily met. Solutions exist - Metall
for mass transfer treating that meet the ever-changing - Plastic
needs of refiners and others to satisfy the tightening reg-
ulations on the fuels market. The goal for any end user is Software and
to determine the right type of mass transfer equipment for
Consulting
their service.

FIBER FILM, FFC Plus, THIOLEX, and REGEN are marks of Merichem
Technologies.
Get in touch:
Mark Knobloch is Technical Services Manager for Merichem
Technologies, overseeing engineering specialists and providing tech- info@vff.com
nical service support for pre-commissioning, start-up, and ongoing
support of Merichem Technologies’ licensed treating processes. He
www.vff.com
holds a BS in chemical engineering from the University of Texas,
Austin. Knobloch is a certified PHA leader from the Process Safety Check out:
Institute, has several standard safety certifications, and is a Registered
Professional Engineer with the State of Texas.
Image Movie VFF
Email: mknobloch@merichemtech.com
Vereinigte Füllkörper-Fabriken GmbH & Co.KG, P. O. Box 552,
56225 Ransbach-Baumbach, Germany, +49 26 23 / 895 - 0

www.digitalrefining.com

Merichem.indd 29 09/12/2024 17:04:41

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ITW Online Cleaning clean an entire Unit in as little as 24 hours on a feed-out/feed-in basis.
ITW Onstream Cleaning clean an entire Unit during the run.
Our proprietary chemistries dissolve and stabilize any asphaltenic/paraffinic/polymeric deposits, by transforming the same into a fully
reusable/reprocessable liquid.
When applied to tank cleaning, our technologies effectively, safely and quickly recover oil from sludge, thereby eliminating waste generation
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itw.indd 1 09/09/2022 11:49:53

 Desalter optimisation strategies:
Part 2
Analysis and optimisation strategies implemented for a two-stage desalter
processing light to medium API crude blends at a Southeast Asian refinery
Venkatesan Mani
Veolia Water Technologies and Solutions

A
s discussed in Part 1, published in PTQ Q4 2024, medium API) is pumped to the crude distillation unit (CDU).
crude oil desalting plays a pivotal role in refinery The feed undergoes preheating in a cold preheat train to
operations by removing salts and impurities that can a targeted desalter temperature of 138-145°C to reduce
wreak havoc on downstream equipment through corrosion, viscosity. The feed is evenly distributed to the two-stage
fouling, catalyst poisoning, and product quality degradation. electrostatic desalters in Trains A and B (see Figure 1).
Despite significant technological advancements in desalter At the crude unit battery limit, a wash water concentra-
design, optimising desalter performance remains an intricate tion of 2.5-3.0% is introduced, while 4.5-5.0% is fed before
challenge due to the complex interplay of multiple factors, the mix valve. The wash source is a blend of raw water and
including crude oil composition, operational conditions, stripped sour water. The crude and water are mixed in the
equipment design, and chemical treatment. This interde- first-stage mix valve at a pressure drop of ~1.2-1.4 bar,
pendence among factors often hinders achieving overall while the second-stage mix valve operates at a pressure
performance goals through isolated optimisation efforts. drop range of ~0.8-1.0 bar. The resulting emulsion down-
stream of the mix valve facilitates the removal of water-sol-
Optimisation of key parameters: Southeast Asian uble impurities from the crude.
refinery case study The water-in-oil emulsion is distributed between the elec-
Desalter operation overview tric grids at an applied field of 150 kilovolt-amps (KVA) with
From the crude tank farm, the feed crude blend (light to an operating voltage of 400-360 volts and an amperage of

Train A
Embreak* Level Level Desalter crude
primary control Transformer control Transformer
demulsifier
3 to 5 ppm

1st stage 2nd stage

Mix valve
Embreak*
1 to 3 ppm
Mix valve
2nd stage water to 1st stage
Crude
tank Brine H2O Ex.

Stripper SWS wash water to 2nd stage ProChem* pH modifier Effluent water Train A

ProChem* solids wetting agent

3 to 5 ppm Train B
Embreak* Level Level
primary control Transformer control Transformer
demulsifier
3 to 5 ppm

1st stage 2nd stage

ETP
Embreak* Mix valve
1 to 3 ppm
Mix valve
2nd stage water to 1st stage
Brine H2O Ex.
ProChem* pH modifier
Stripper SWS wash water to 2nd stage Effluent water Train B
ProChem* solids wetting agent
3 to 5 ppm

Figure 1 Desalter process flow diagram

www.digitalrefining.com PTQ Q1 2025 31

Veolia.indd 31 09/12/2024 17:17:06

 Crude Stability Model Output
RELATIVE INSTABILITY INDEX (RX)
Parameter Value
Stable Unstable Critical Severe

Severity
RIX 1.70 –
<1.5 1.5 - 3.0 3.0 - 6.0 6.0 - 10.0
CPI 3.93 –
Stabiliser 2168
Demand <5 ppm* Stable emulsion, oily water & solids

Unit Issues
Potential
API Gravity 31.3 ˚ Desalter
Viscosity 11.0 cSt
Cold preheat, Hot preheat & Heater fouling
TAN 0.3 mg KOH/gm
Sulphur 1.8 % w/w
FOULING POTENTIAL INDEX (FPX)
YC7-Asphaltenes 2.1 % w/w
<1.0 1.0-2.0 2.0-3.0 3.0 - 6.0 6.0 - 10.0

Severity
YSaturates 51.9 % w/w
Low Moderate Medium Critical Severe
YAromatics 31.8 % w/w
YResins 10.6 % w/w
Conventional Fouling Unconventional Fouling
YC5-Asphaltenes 5.6 % w/w

Unit Issues
Potential
YCII 1.4 – Hot Preheat fouling
True RIX 1.7 –
Heater fouling
*Based on total charge rate

Figure 2 CrudePlus study: crude stability and emulsion and fouling predictions

80-120 amps for most crude blends. The design residence basic sediment and water (BS&W) as free water, with 8%
time for the desalter is 12 minutes for crude oil and 160 wash water and <12 ppm chloride in the wash water.
minutes for water. The crude oil inlet is designed for 20 PTB salt and 0.5
The dosage strategies followed split feed technologies.1 vol% BS&W. However, most of the crude blends processed
The proprietary emulsion breaker (Embreak) feeding rate have a salt concentration of <10 PTB. Chloride in the over-
will be 5-10 ppm, with the dosage split into two locations: head is controlled to <30 ppm without any caustic injection
one before the cold preheat and another at the mix valve into the desalted crude, ensuring sodium levels are main-
of each stage. The solids wetting agent feed rate will be tained below 1 ppm in the atmospheric residue.
3-5 ppm based on incoming crude solids (>60 ppm in raw The following section covers the basics of key parame-
crude). These chemistries help reduce interfacial film ten- ters and how each key parameter optimisation approach
sion, promoting oil and water separation. was followed, considering interdependent variables.
The desalted crude achieves the key performance indica-
tors (KPIs). Specifically, it achieves a crude outlet salt con- Crude oil characteristics and benchmarking study
centration of <0.5 per thousand barrels (PTB) and 0.2 vol% Any desalter optimisation strategy begins with under-
standing the characteristics
Feed crude characteristics study of the crude oil before moving
on to operational parameter
Results Ref method optimisation. A detailed crude
Feed crude API 29.6 ASTM D287-22
blend quality analysis was
Viscosity at 40C, cst 10.73 ASTM D7945-21a
conducted periodically based
Total chloride, ptb 8.0
on crude blend changes and
Inorganic chloride, ptb (extractable) 7.9 ASTM D6470
whenever KPIs were not in
Organic chloride, ppm (non-extractable) <1 ASTM D4929-19a
control for any short period.
Solids in crude, ptb 104
The crude characterisation
Filterable solids, ptb (>0.42 micron) 104 ASTM D4807-88
testing focused on desalter
Iron, ppm 4.3 XRF*
Crude compatibility
impact variables, such as
RIX – Relative instability index 1.7 CrudePlus* crude oil API/density, vis-
CPI – Crude precipitation index 3.9 CrudePlus* cosity, salt content, water
FPX – Fouling potential index 2.02 CrudePlus* content, metal content, con-
Crude emulsification study ductivity, compatibility, foul-
Emulsification tendency High PED ing potential, and filterable
Emulsification precursor Iron/filterable solids PED solids.
Emulsion resolved with solids wetting agent Synergistic performance PED An emulsion potential study
was also conducted using
Table 1 a portable electric desalter

32 PTQ Q1 2025 www.digitalrefining.com

Veolia.indd 32 09/12/2024 17:17:06

 Emulsion breakers screening (8% wash water) Emulsion breakers screening (5% wash water)
100 100
Demulsification efficiency (DE), %

Demulsification efficiency (DE), %

90 Embreak 2W157i 5 ppm 90 Embreak 2W157i 5 ppm
Embreak 2W157i 9 ppm Embreak 2W157i 9 ppm
80 80
Embreak 2W197i 9 ppm + Embreak 2W197i 9 ppm +
70 Embreak 2163 3.5 ppm 70 Embreak 2163 3.5 ppm

60 60
50 50
40 40
30 30
20 20
10 10
0 0
BLANK Embreak 2W157i BLANK Embreak 2W157i

Figure 3 Emulsion stability test study using portable electric desalter

(PED) to validate process operating conditions and opti- standard viscosity temperature charts for liquid petroleum
mise chemical dosages for the emulsion breaker and solids products (D341 Chart VII).
wetting agents. The impacts of wash water quality, pH, and It is important to remember that emulsion viscosity
chlorides were also assessed. Additionally, desalter emul- increases exponentially with lower temperatures, particu-
sion layer samples were analysed when there was growth larly in oil-water emulsions with varying water-to-oil ratios,
in the desalter emulsion layer. The brief test results are as referenced in emulsion journals. Typically, emulsion vis-
summarised in Table 1. cosity >100 centipoise will lead to a stable emulsion layer
Crude samples were subjected to compatibility and foul- in the desalter. Increasing the emulsion breaker dosage can
ing assessments using field-proven technologies, such as help resolve short-term issues. However, with intense sol-
the proprietary CrudePlus tools (see Figure 2). ids and destabilised asphaltenes stabilisation conditions,
The emulsification tendency of the crude was evaluated increasing temperature will be the best approach for long-
in the PED. The crude was confirmed to have high emulsion term sustainable operations. Hence, without temperature
potential based on poor water separation with no chemi- optimisation based on crude viscosity, optimisation of other
cal treatment. With the right emulsion breaker dosage, the parameters will not help achieve consistent KPIs.
emulsion broke down, and water separation was observed Another limitation of high desalter temperature operation
with treatments using solids wetting agents. These results will be an increase in water solubility in the desalted crude
were used for desalter optimisation, as shown in Figure 3. oil. To retain the BS&W <0.3 vol% in the desalted crude
and keep the viscosity in control, the desired desalter oper-
Desalter temperature ating temperature target was >138-145°C, where Figure 4
Desalter temperature = f {crude oil viscosity and density, shows the results achieved after temperature optimisation.
water solubility in the crude} Predominantly, refineries often report total BS&W <0.05
To achieve maximum desalting efficacy, a widely followed vol% in desalted crude, even at high desalting tempera-
approach is to increase the desalter temperature, which can tures. The low BS&W is subject to debate based on the fact
enhance salt removal efficiency. However, this method typ- that 60% is due to sampling errors (such as hot sampling of
ically adopted and pushed the desalter’s maximum oper- desalted crude without proper cooling), 30% is due to the
ating temperature limit (typically 155°C) or the limit based lack of water solubility at the desalter operating tempera-
on the transformer bushing design temperature and some- ture, and 10% is due to other analytical factors. Therefore,
times corrosion risk limits. While higher temperatures can it is important to validate the BS&W in desalted crude with
reduce crude oil viscosity and aid water separation, beyond the water yield in the overhead based on different sources
certain temperature increases, water yield diminishes the rather than solely relying on BS&W analytical results, as
returns in separation efficiency. Hence, increasing to the shown in the following example:
maximum desalter temperature is not a cure-all and comes BS&W in desalted crude = Water yield in CDU overhead
with limitations and risks. boot – CDU column stripping steam – CDU side cuts
Temperature optimisation often starts based on the rec- steam – Overhead wash water before coolers.
ommended operating viscosity of the desalter. Even though
there are no well-defined design limits for desalter operat- Mix valve DP
ing viscosity, the desalter is targeted to operate at a viscos- Mix valve ΔP = f {crude characteristics, temperature,
ity <2 cSt based on best practices guidelines for effective wash water, electric grid, interface level}
desalting. Hence, with the analysis of crude blend viscosity The function of the mix valve extends beyond simply mix-
and API, the temperature required to achieve the desired ing crude oil and water. It is designed to control the water
operating viscosity can be estimated from the ASTM population, droplet size, and distribution within the crude

www.digitalrefining.com PTQ Q1 2025 33

Veolia.indd 33 09/12/2024 17:17:06

 emulsions are less stable. Efficient desalter designs require
160 0.80 less wash water. To achieve stringent salt content targets,
such as salt <0.5 PTB in desalted crudes, a higher percent-
155 0.70
age of wash water of up to 10% is needed. Deploying <3

% BS & W in desalter crude

Desalter temperature (˚C)

150
Temp > 150 ˚C
0.60 vol% wash water drastically affects desalter performance.
145
BS & W > 0.45 vol%
0.50 It is recommended to split the wash water feed rate at
Temp < 145˚C
BS & W < 0.3 vol% the crude battery limit, specifically before the cold preheat
140 0.40
exchanger (to prevent solids fouling in the cold preheat
135 0.30 and increase the contact time between crude and water to
130 0.20 effectively remove upstream chemical-based crude impu-
Post mix valve
optimisation rities) and upstream of the mix valve. Stripped sour water,
125 Desalter temperature 0.10
Water yield from crude BS & W free from chloride (<10 ppm), dissolved oxygen <7 ppb, no
120 0.00 dissolved carbon dioxide, and pH 7-8, is best for desalting
operations.
Figure 4 Water carryover in desalted crude vs temperature While higher wash water percentages improve desalting,
the availability of wash water sources from plant overhead
oil, effectively washing salts from the crude. Globally, stripped sour water is also limited. An increase in desalter
globe valves are the most common mix valves deployed for wash water increases effluent generation and treatment
desalters due to their precise control, versatility, durability, costs in the wastewater treatment plant. In crude desalting,
reliability, and ease of maintenance. Mix valves typically it is important to remember that salt removal from 10 PTB
accommodate pressure drops ranging from 10 to 50 psi. to <2 PTB will be comparatively simpler than achieving a
For light to medium API crude, the recommended pressure reduction of salt from 2 PTB to <0.5 PTB.
drop operation is 10-35 psi (0.8-2.4 bar). Too low produces At low salt levels, specifically <2 PTB with 8% wash
more coarse droplet sizes, leading to poor desalting, and operation conditions, the conductivity of water droplets
too high produces fine droplet sizes that can make the dispersed in crude will be low. This leads to a poor force
emulsion difficult to break. of attraction between water droplets, compromising water
The droplet size and distribution are not limited to the coalescence efficacy. Hence, maintaining a minimum con-
pressure drop in the mix valve. They depend on the elec- ductivity of 1,000 µS/cm in the desalter outlet brine water
tric field, temperature, wash water, and crude density.2 In is crucial to ensure a healthy force of attraction between
refinery day-to-day desalter optimisation, simple baseline the particles.
monitoring of salt outlet vs mix valve DP will help establish When the desalted brine conductivity ranges from 2,000
the safe operating range for the mix valve DP. to 5,000 µS/cm, water carryover in the desalted crude
The best practices followed for operating the two-stage ceases, and consistent salt removal efficiency is achieved.
desalting mix valve include: Hence, it is important to monitor the conductivity of the
u Operate the first stage of the desalter at a high-pressure desalter brine water from each stage of the desalter for a
drop to achieve intense mixing, maximising the removal of holistic desalter optimisation approach. With all the previ-
salts during the desalting process. ously noted best practice adoptions, deploying low chloride
v Operate the second stage at a relatively lower DP to pro- wash water (<10 ppm) with a wash water rate of 4.5-5%
mote dehydration, ensuring that all the salt-washed water at the mix valve led to achieving the salt outlet KPI (see
carried from the first-stage crude will be fully dehydrated. Figure 6).
Figure 5 illustrates how to achieve the desired crude The desalter brine pH is equally important compared
salt outlet range with a sharper interface layer at high to the wash water pH for overall desalter performance.
voltage and low amperage conditions in the electric grid. Operating the brine pH slightly towards the neutral to
This ensures there is no fine emulsion formation and water slightly acidic side (6-7) is recommended for effective
carryover in the desalted crude. Best practices such as desalting operation, as it helps minimise the corrosion envi-
mix valve calibration, check valve opening, and actuator ronment. High pH in the wash water and desalted brine can
response were adopted annually for reliable mix valve deprotonate emulsifying agents, enhancing their ability to
operations. For high solids crudes processing timeframes, stabilise water droplets in oil.
the mix valve was cleaned every two years to remove any For crudes with chemical impurities like phosphate
deposits around the valve positions. esters, amine chlorides, calcium naphthenates, or sodium
naphthenates, it is recommended to operate the desalter
Wash water brine pH slightly acidic (5-6) to wash away these impurities
Wash water = f {wash water %, wash water quality, salt in the desalter brine. It is important to inform the down-
& BS&W, electric grid, brine pH, chemicals} stream wastewater treatment plant to monitor chemical
A common industry practice is to deploy 3-10% wash water oxygen demand (COD) control, as it can increase with low
relative to the volume of crude oil.3 Typically, medium to pH operations. To overcome this issue, a pH modifier with
heavy crude oils require more wash water (6-10%) due to a corrosion inhibitor, such as Prochem or Predator, was
higher viscosity and stable emulsions, while lighter crudes deployed to control brine pH.
(4-6%) need less wash water as they are less viscous and In case service water or raw water is used as wash water

34 PTQ Q1 2025 www.digitalrefining.com

Veolia.indd 34 09/12/2024 17:17:06

 C

CM

MY

CY

CMY

092_Q4_HEXXCELL.indd 1 13/09/2024 09:48:42

 1.40 3.00 3.0 7.0%

1.20 2.50 6.0%

2.5

1.00
Mix valve DP (bar)

5.0%

Wash water (%)

Delta b/w first &
second stage 0.2 bar 2.00 2.0

Salt out (ptb)

Salt (ptb)
0.80 4.0%
1.50 1.5
Post adopted strategy of Consistent 5 to 4.5 vol% of wash water
0.60 1st stage mix valve high DP (Desalting focus) into mix is key for effective desalting, 3.0%
2nd stage mix valve low DP (Dehydration focus) helped to achieve salt <0.5 ptb
1.00 1.0
0.40 2.0%

0.20 0.50 0.5 1.0%

0.00 0.00 0.0 0.0%

Train A - 1st stage Train A - 2nd stage Train A Salt out, Ptb Train A - Salt out, Ptb Train A - 1st stage Train A - 2nd stage
Mix valve DP, bar Mix valve DP, bar Wash water % Wash water %

Figure 5 Mix valve strategies for two-stage desalter Figure 6 Wash water per cent vs salt outlet

during refinery CDU start-up or due to stripped sour water All desalter designers commonly provide three to five
challenges (which is not recommended for long-term use), interface layer sample points, with 6in between each sam-
high levels of dissolved CO₂ and O₂ in the raw water can ple point. Typically, emulsion layer growth of more than 6in
acidify the desalter brine. Sulphur-rich crudes produce in the desalter vessel indicates strong emulsion formation,
more acidic byproducts, and higher desalter temperatures which significantly compromises the crude oil and water
accelerate oxidation reactions, increasing the acidity of the residence time in the desalter. This affects the efficacy of
desalter brine water. The desalter experienced a pH drop the desalting process and can create uncertainty, leading to
of 1.5-3 units while using raw water during high sulphur slugs of salt and water entering the desalted crude under
crude processing periods. The pH modifier Prochem was the event of small disturbances, causing fouling in down-
used to maintain the brine pH at 6-7 and sustain desalter stream heat exchangers.
performance. The best operating guidelines for interface level adjust-
ment for two-stage desalters are:
Interface level u Target the first-stage desalter operation at a higher
Interface level = f {try-line emulsion thickness, residence interface level (60-70%). It will increase the water phase
time, chemical dosage, mix valve, solids in crude, mud residence, helping to control oil carryover in the brine.
wash} v Target the second-stage desalter operation at a lower
The term ‘interface level’ in a desalter specifically refers interface level (40-50%). It will increase the crude resi-
to the boundary between the water and emulsion/oil lay- dence time, helping to prevent water carryover in the crude.
ers. Interface level and residence time are interdepend- Upon adopting these shared operating guidelines, the
ent parameters. A rising interface level often indicates salt outlet was in control, as the oil in brine remained <100
the growth of the emulsion layer. Hence, monitoring the ppm (within the design limit) 100% of the time.
interface level is critical, and it helps achieve the desired The presence of solids, such as clay particles, and heavy
residence time for both oil and water phases. Regular mon- organic compounds, like asphaltenes, can stabilise emul-
itoring can help identify trends and patterns in emulsion sions, creating a complex, heterogeneous layer that results
formation. An increased pressure drop across the desalter in challenges in interface level measurement. From the
can indicate the presence of a thick emulsion layer, causing literature and lab PED experiments, it was learned that
resistance to flow. Also, high chemical consumption often solids-stabilised emulsions have relatively high viscosities
correlates to a lack of proper interface monitoring. and densities compared to typical oil-water emulsions
Combining interface level measurements with other oper- without solids. This heterogeneity can confuse measure-
ational parameters like pressure drop and chemical usage ment devices. Hence, preventing solids stabilisation at the
is recommended to get a comprehensive view of emulsion desalter interface layer is crucial, as it poses challenges in
behaviour. Advanced capacitance and gamma densitome- interface level measurements. Controlling interface emul-
ters can provide detailed profiles of the layers within the sion layer solids to <1,000 ppm is critical to prevent solids
desalter. Therefore, conducting periodic visual inspections pickering stabilisation.
through try-line/try-cock sampling points to validate the As shown in Figure 7, a real-time study on desalter emul-
accuracy of interface measurement (as shared in detail in sion layer solids stabilisation helped to understand the sol-
the troubleshooting section) is crucial. ids distribution and growth of the emulsion layer in both
Typically, desalter try-line sample visual validation is the first and second stages. During this solids stabilisation,
the first step in desalter troubleshooting. Any deviations the interface level measurement showed 10-15% devia-
in measured vs observed levels in try-lines should be tions from the actual desalter level observations in the try-
addressed as part of the troubleshooting approach dis- line sample points. Figure 7 is a graphical representation
cussed in Part 1 of this article. of where samples were taken and the solids ppm levels at

36 PTQ Q1 2025 www.digitalrefining.com

Veolia.indd 36 09/12/2024 17:17:06

 Train A (First stage) Train A (Second stage)
Oil collection header
Oil phase

5
9138 ppm Distributor
11986 ppm 5
4 4
3 Interface 3
685 ppm
2 2 1289 ppm
1 1
Water phase

Crude in 104 ppm

Train B (First stage) Train A (Second stage)

Oil collection header
Oil phase

5 2952 ppm Distributor

4 16680 ppm 5
3 4 1396 ppm
Interface 3
2
1 2 4318 ppm
Water phase 1

Crude in 104 ppm

Sample No. Description Filterable solids, ppm Ca, ppm Fe, ppm Ni, ppm S, wt% V, ppm
1 Feed crude 104 3.1 4.26 10.88 2.451 31.93

Desalter
Train A

2 First stage 11986 50.46 1590.1 14.43 1.945 26.92

3 First stage 9138 37.79 1151.3 13.89 2.077 28.92

4 Second stage 685 8.6 52.8 10.54 2.29 29.75

5 Second stage 1289 9.4 97.4 10.88 2.33 29.84

Desalter
Train B

6 First stage 16680 336.6 8090.3 41.54 2.163 58.85

7 First stage 2952 11.08 361.6 10.62 2.157 27.49

8 Second stage 4318 97.85 3413 49.3 2.70 15.85

9 Second stage 1396 13.84 450 14.88 2.276 30.04

Figure 7 Solids stabilisation influence on interface layer

the interface layer. The bottom picture is a detailed compo- • pH modifiers: These are selected and applied in wash
sition analysis of the emulsion layer to explain the nature water based on the desalter brine pH ~6-7. This will also
of solids stabilisation. Hence, monitoring the interface level help prevent corrosion from low pH and improve the effi-
during every crude blend change or crude tank changeover ciency of salt removal.
is critical for holistic desalter optimisation. The strategies adopted for chemical optimisation include:
• Selection and dosage: Figure 8 shows the PED study
Desalter performance chemicals results. Regularly analysing crude oil quality and emulsion
Desalter performance chemical = f{try-line emulsion studies using a PED helps study different chemistries and
thickness/interface level, electric grid, mix valve, temper- downselect the best demulsification agents. The right dos-
ature, wash water quality, solids in crude} age rates of 5-10 ppm are applied to achieve 100% oil and
A comprehensive chemical treatment programme is crucial water separation within the desalter residence time.
for optimising crude oil desalting processes in refineries. • Monitoring and adjustment: Continuous monitoring of
This programme typically includes the use of demulsifiers, desalter performance and adjusting chemical dosages as
wetting agents, and pH modifiers as follows: needed to maintain the interface emulsion layer thickness
• Demulsifiers: It is recommended to evaluate and select below 6in.
the Embreak chemistry based on the emulsion separation • Troubleshooting: Time-to-time optimisation of pH
study with a PED to mimic real-time desalter functionality modifiers to control brine pH plays a critical role in trou-
• Solids wetting agents: These are crucial for crude con- bleshooting. Measuring solids at the interface and main-
taining more than 60 ppm filterable solids taining levels below 100 ppm are necessary to prevent

www.digitalrefining.com PTQ Q1 2025 37

Veolia.indd 37 09/12/2024 17:17:07

 PED study with 8% wash water @ 3 KVA PED study with 5% wash water @ 3 KVA
8.0 5.0
Blank Blank
7.0 Embreak 2W157i (9) Embreak 2W157i (3)
Water separation from crude oil

Water separation from crude oil

Embreak 2W157i (9) 4.0 Embreak 2W157i (9)
6.0 + Embreak 2163 (3.5) Embreak 2W157i (9)
+ Embreak 2163 (3.5)
5.0
3.0

4.0

2.0
3.0

2.0
1.0
1.0

0.0 0.0
0 1 2 4 6 8 16 32 0 1 2 4 6 8 16 32
Residence time (minutes) Residence time (minutes)

Figure 8 PED study with emulsion breaker, wetting agent, and wash water per cent change

emulsion layer growth. Mostly, split dosage of demulsifi- Asian refinery, the applied power from the transformer is
ers into the battery limit and at the mix valve is of prime 150 KVA with a designed applied voltage of 400 volts and
importance for desalter optimisation. a frequency of 50 Hz. The surface area under the grid is
Figure 8 explains how the emulsion separation study 60 m². Hence, the applied electric field will be 2.5 KVA/m².
helps to understand the emulsion’s stability without chem- Since the applied electric field is within the recommended
icals. The emulsion stability reduces with chemical optimi- range of best practice windows, with brine conductivity
sation, with an increase in 5-8% wash water. An increase (water droplets in the crude) in the range of 2,000-5,000
in dosage with solids wetter helped resolve the emulsion micro Siemens (discussed in detail in the wash water sec-
100% within the given residence time of the desalter. tion), good desalting efficacy could be achieved for light to
medium API crude blends operation periods without many
Electric grid challenges. Based on monitoring, the desalter could oper-
Electric grid = f {crude conductivity, brine conductivity, ate at the recommended voltage of 400-380 volts and an
interface level, water solubility in crude, temperature} amperage of 80-100 amps.
The electric grid is responsible for inducing dipole moments For more than two years, the desalter targeted perfor-
in water droplets dispersed in the crude oil, promoting the mance has been consistently achieved and sustained, with
coalescence of small water droplets into larger droplets, >90% performance indicators. Specifically, the desalted
which can then settle out of the oil due to gravity. The elec- crude salt has consistently remained <0.5 PTB, the over-
tric grid acts as the heart of electrostatic desalter operation. head chloride levels have been limited to <30 ppm without
High voltage is necessary to create a strong electrostatic caustic dosage in the desalted crude, and controlled sodium
field. The voltage should be maintained at the design spec- levels in the atmospheric residue have been controlled to
ifications to ensure effective coalescence, and monitoring <1 ppm to prevent downstream ARHDT catalyst poisoning.
amperage is equally important. Excessive amperage can To recap briefly, following a systematic optimisation
indicate issues such as short-circuiting, which can damage strategy is crucial. More importantly, focusing on day-to-
the grid and reduce its effectiveness. day monitoring, validating the desalter performance during
Also, high operating temperatures can affect the perfor- each blend change and crude tank farm change operation,
mance of the electric grid and the dielectric properties of the and slop oil management will lead to proactive optimisation
crude oil. Hence, optimal temperature is crucial to ensure the towards operational and chemical factors. Also, do not for-
grid operates within safe limits. In the desalter operation, get to conduct periodic data analysis with basic statistical
the emulsion produced by the mix valve is distributed via or desalter benchmarking tools, which will be key to identi-
the crude distributor between the electric grids. Between fying the influencing parameters.
70% and 90% of primary water coalescence occurs within
a few seconds under the applied electric field. Secondary Conclusion
coalescence occurs beyond the electric grid, where larger The cost of poor desalting is significantly high. From the
coalesced water droplets continue to settle due to gravity, desalter survey, it is evident that crude blend quality varia-
contributing significantly to overall water removal. Hence, tions drive the day-to-day desalter key parameter optimisa-
emulsion growth control, specifically interface monitoring, tion using basic data analysis tools. The brief overview and
is critical to control desalter upsets. key performance factor optimisation strategies followed in
The applied electric field for light to medium API crudes this real-time refinery case study exemplify the critical role
will be ~1-3 KVA/m². For the desalter in the Southeast of strategic parameter management in refining operations.

38 PTQ Q1 2025 www.digitalrefining.com

Veolia.indd 38 09/12/2024 17:17:07

 Adopting a holistic approach to operational parameter challenges of crude oil desalting, minimise the associated
optimisation, integrated with the best chemical treatment costs, and achieve sustained operational excellence, even
programme, enabled the refinery to consistently meet in dynamic market conditions.
desalter performance indicators. This ensured sustained
operational excellence and profitability in a dynamic refin- Acknowledgment
ery market environment. The key takeaways from this case The author would like to express his gratitude to the Veolia team, includ-
study include: ing Mike Dion, Sumalya Nag, Nimesh Kumar Patel, Martin Willis, Ching
• Understand the interdependencies among factors like Yaw Lee, and Piravin Mageswaran, for their valuable contributions.
crude quality, operating conditions, equipment design, and Special thanks go to the Southeast Asian refinery CDU Process Manager
chemical treatment in desalter optimisation. and Specialist Distillation team, Saiful Dzulfitri, Azamuddin Jameran, Nor
• Establish safe operating boundaries for critical parame- Atifah Binti, and Chua Wee Kheng, for their intense support and motiva-
tion during the on-field troubleshooting and optimisation activities.
ters through data analysis, troubleshooting discrepancies,
and periodic calibrations.
References
• Optimise key parameters synergistically, considering their
1 Dion M, Desalting opportunity crude, NPRA Spring National Meeting,
interdependencies (for example, temperature for viscosity
March 1995.
and water solubility, mix valve DP for droplet size and dis-
2 Desalter Training Manual, Veolia Water & Process Technologies.
tribution, wash water for conductivity and coalescing force,
3 Gutzeit J, Controlling unit overhead corrosion: rules of thumb for bet-
interface level for residence time and emulsion control).
ter crude desalting, Paper no. 07567, Corrosion 2007.
• Implement a comprehensive chemical treatment pro- 4 Shooshtari M, Karimi M, Panahi M, Modelling of an industrial mixing
gramme, including demulsifier selection, wetting agents, valve and electrostatic coalescer for crude oil dehydration and
and pH modifiers, based on emulsion studies and brine desalination, Separation Science & Technology 2023, Vol 58, No.7,
chemistry. pp.1,306-1,318.
• Continuously monitor performance, validate results dur-
ing crude changes, and make proactive adjustments to Venkatesan Mani is Senior Product Manager and Application Expert
operational and chemical factors. for Veolia Water Technologies and Solutions for Southeast Asia and
• Leverage basic statistical tools and benchmarking for iden- Oceania region, responsible for speciality chemical solution design and
tifying and addressing influencing parameters periodically. application expertise in refinery and petrochemical process technolo-
• By following a systematic optimisation approach and gies. Mani holds a BTech in chemical engineering from Anna University,
integrating best practices, refineries can overcome the Chennai, India.

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 Optimising shell and tube heat
exchanger operation
Case studies show how inserts improve heat transfer coefficients, mitigate fouling and
reduce end-of-run pressure drop, as demonstrated with the preheat train of a CDU

Nicolas Aubin
Petroval

S
everal studies published by Total Energies and oil preheat trains caused by asphaltene deposition and/or
Petroval have examined the improvements that can coke formation on hot surfaces.
be obtained from tube inserts in heat exchangers. In these tests, heat exchangers forming part of preheat
The benefits of using a combination of tube insert tech- trains in three refineries were equipped with new inserts.
nologies are manifested in extended run lengths between Their performances were monitored over two to four years,
cleaning shutdowns, an increased heat transfer coefficient, depending on the circumstances, and compared to the
a reduced fouling rate, and stability of pressure drop. durations of previous runs in similar process conditions.
From an economic viewpoint, the payback is achieved The improvements in heat transfer and the impact on CO2
within a few months from four sources of improvements: emissions will be further highlighted.
the preheat train energy saved (by the increase in the
heat transfer), the reduction in maintenance cost (reduced Fouling reduction case studies
cleaning frequency), the increased throughput, and positive Case A – Rotational effect
environmental impact stemming from the reduction in CO₂ The Turbotal rotating device is hooked onto a stationary
emissions (as a consequence of the better heat transfer head and installed at the inlet end of the heat exchanger
performance). Indeed, a very substantial benefit can be tube (see Figure 1). This system is a continuous online
obtained if a unit is bottlenecked by a heat transfer limita- cleaning device, the purpose of which is to reduce the foul-
tion or the furnace. ing layer at the tube walls by means of a mechanical effect.
The device uses the energy of the flowing medium in the
Technology limits tubes to achieve rotation at around 1,000 rpm during the
Limiting the carbon footprint is now essential to achieve net- whole run duration. This rotation speed is determined at
zero emissions in the oil industry by 2050. This ambitious the design stage by the mechanical design of the Turbotal
target will require large investments in new technologies and issued from correlations determined on experimental
for heat transfer efficiency and carbon capture. However, skids.
the technologies that will be required in the future are not The extra pressure drop generated is typically in the
yet available at an industrial scale; time is needed for their range of 100 millibar per pass at a flow velocity of 1.0 m/s,
maturation, investment, and timely operation. with a lifetime limited to three years due to mechanical
The oil industry relies mainly on preheat shell and tube heaterosion of the parts. The last two pairs of heat exchang-
exchangers to reduce the amount of firing required in fired ers just before the furnace were suffering from severe
furnaces. However, the performance of these exchangers is fouling over a period of less than one year. All four heat
often limited by fouling and mechanical designs
not upgraded to the required level of operation. Heat exchangers used in Case A –
There are tube insert technologies available on design and operating conditions
the market that offer a quick solution to enhance
Position in the train Just before the furnace
the performance of shell and tube exchangers. Number of bundles 2 branches of 2 bundles
These provide immediate improvements in heat No. of tubes per bundle 626
transfer from start of run (SOR) with no mod- Tube length 6,100mm
ifications to the exchangers or the operating OD/BWG 1”/12
conditions. Product tube/shell side Crude/atmos residue
Flow rate (tube side) 260/330/430 t/h
The benefits of using tube insert technologies
Flow velocity (tube side) 1.0 to 1.70 m/s
were previously demonstrated in terms of an Tube inserts Turbotal
increased heat transfer coefficient1,3, reduced Replacement frequency Every 2 to 3 years
fouling rate,2 and stability of pressure drop. This Figure 1 Turbotal on a
current study will only consider fouling in crude tube bundle Table 1

www.digitalrefining.com PTQ Q1 2025 41

petroval.indd 41 09/12/2024 17:25:02

 Heat exchangers used in Study B –
design and operating conditions

Position in the train Just before the furnace

Number of bundles 2 bundles in parallel
No. of tubes per bundle 600
Tube length 6,100mm
OD/BWG 1”/12
Product tube / shell side Crude/bottom P/A
Flow rate (tube side) 431 t/h design
Flow velocity (tube side) 1.87 m/s
Tube inserts Spirelf
Replacement frequency Every 3 years

Table 2

exchangers were equipped with Turbotal Figure 2 Spirelf on a tube bundle Figure 3 Fixotal devices in the heat
and operated in the same range of process exchanger
conditions as previously (see Table 1). The
monitoring of the performance was then compared to the system significantly increases shear stress at the wall, pre-
previous data; the comparative trend of the outlet temper- venting product stagnation in the boundary layer adjacent
ature will be presented in the results section. to the tube. The purpose of this fixed device is mainly to
increase the rate of heat transfer by renewing the boundary
Case B – Vibrational effect layer at the tube wall, with an appreciable side effect on
The Spirelf vibrating device is fixed on both tube ends by a fouling mitigation, including certain types of fouling linked
fixing wire (see Figure 2). This system also serves as a con- to wall temperature, such as polymerisation, paraffin solid-
tinuous online cleaning device, reducing the fouling layer on ification, scaling, and crystallisation.
the tube walls by means of a mechanical effect. The extra pressure drop generated by the device is
The vibrating device uses the energy of the flowing typically in the range of 200 millibars per pass for a flow
medium in the tubes to convert it into vibrations of the velocity of 1.0 m/s. An example of Fixotal installed in a tube
device, both radial and longitudinal. The extra pressure bundle is presented in Figure 3 to illustrate the device once
drop generated by the device is typically in the range of 200 installed.
millibars per pass for a flow velocity of 1.0 m/s. The lifetime The chosen case study will review the performance of a
of the device is limited to six years since it must be removed complete preheat train of 12 heat exchangers that are all
and replaced at each turnaround for internal cleaning and operated with the same fluids. Crude is flowing on the shell
inspection of the heat exchanger tubes. side from the desalter to the furnace, and atmospheric res-
The last pair of heat exchangers, just before the furnace, idue is flowing counter-current on the tube side from the
suffered from severe fouling over a period of less than one tower towards the beginning of the hot train.
year. The two heat exchangers were equipped with Spirelf Only the last three exchangers out of the 12 were
and operated in the same range of process conditions as equipped with Fixotal technology and operated in the same
previously (see Table 2). The monitoring of the performance range of process conditions as previously (see Table 3). The
was then compared to the previous data. The comparative monitoring of the performance was then compared with
trends of the duty achieved and the flow rates will be pre- the previous data; the comparative trends of the overall
sented in the results section. heat transfer coefficient (OHTC) and duty will be presented
in the results section.
Case C – Heat transfer effect Due to a lack of instrumentation, only three temperature
To promote turbulence at the inside tube surface, the Fixotal measurements points were available on each flow pass: at
the inlet, in the middle (after six bundles), and at the outlet.
Heat exchanger used in Study C – Consequently, the improvements achieved in the last three
design and operating conditions heat exchangers were mitigated with the normal perfor-
mance of the other three that were not equipped between
Position in the train Just before the furnace
No. of tubes per bundle 732
the two temperature indicators.
Tube length 5,000mm
OD/BWG 1”/12 Case A results
Product on tube / shell side Reduced crude / crude The trend presented in Figure 4 shows the OHTC
Flow rate (tube side) 134.2 t/h of the four heat exchangers in operation on com-
Flow velocity (tube side) 0.80 m/s
parative runs. The reference run in blue lasted only
Tube inserts Fixotal
Replacement frequency Every 4 years 183 days, with a significant loss of performance as
the OHTC dropped from 230 kcal/h.m² °C at SOR to
Table 3 87 kcal/h.m² °C within this six-month period. After this

42 PTQ Q1 2025 www.digitalrefining.com

petroval.indd 42 09/12/2024 17:25:02

valmet.indd 1 09/12/2024 15:09:49
 Impact on energy savings and CO2 emissions on heat
300
exchangers used in Study A* **
OHTC plain tube
250 OHTC with Turbotal
With Turbotal
Gain on energy recovery (Gcal/yr) 18,200
kcal/h m2˚C

200
Gain on energy recovery (TOE/yr) 1820
Energy savings 1092 k€
150
Gain on CO2 emissions (tons first yr) 5,460
100
Reduction in CO2 emissions 546 k€

50 Table 4
0 100 200 300 400 500 600 700 800
Day
days for bare tubes to 820 days with the rotating device.
The fouling mitigation allowed improved fouling rate con-
Figure 4 Trend of OHTC for both cases with (red) and trol and, consequently, control of heat exchanger perfor-
without Turbotal (blue) in the same flow conditions mance and pressure drop related to the fouling layer, even
though no direct pressure drop measurement was available
a shutdown and mechanical cleaning were required to on these four exchangers.
recover heat transfer on these exchangers. A payback analysis was done on this application to evalu-
The comparison of the first six months with the Turbotal ate the energy gains (see Table 4) compared to the Turbotal
rotating device highlighted the direct benefits that are sum- cost installation, which was in the range of €130,000. The
marised in Table 4 on heat recovery in the range of 1,092 payback calculated by considering only the cost of energy
k€. There was also a significant reduction in the CO2 emis- and the gain on CO2 emissions was about one month.
sions from the furnace, about 560 tons of CO2. Depending However, some other sources of savings should also be
on the location, these emissions can be subjected to taxes considered, such as reduction of maintenance cost (avoid-
at different rates over the world (CO2 emissions are being ance of mechanical cleaning) and production losses (reduc-
taxed at 100 €/ton in Western Europe.) tion of throughput during partial shutdown for cleaning).
In comparison, the run with the rotating device lasted 820
days of continuous operation. The SOR was typically with Case B results
an OHTC of 270 kcal/h.m² °C, which dropped slowly to 150 The trend presented in Figure 5 shows successive runs
kcal/h.m² °C within 300 days and remained in the range of during which the duty (blue trend) was plotted. The refer-
150 to 200 kcal/h.m² °C depending on the flow conditions. ence run, bare tubes, started in November 2014. The aver-
This phenomenon is due to the fouling mitigation during age duty from 30/11 to 22/04 was roughly 36 GJ/h. The
the run. The Turbotal rotating device significantly reduces duty then decreased from roughly 36 GJ/h to 22 GJ/h by 28
the fouling rate but cannot prevent fouling deposition from November 2015, for an average of 30 GJ/h over the entire
occurring. Some previous work identified that fouling resist- reference run.
ance with the rotating device ends up with an asymptotic The drop in duty was about 40% in one year, even though
profile corresponding to the distance between the tube wall the flow rates on tube and shell sides remained very sta-
and the rotating device.4 ble and close to the design case. The flow rate across the
Run lengths were multiplied by a factor of four, from 183 heat exchangers remained close to the design value, which

50
1400
Pumparound and crude flow rates (T/h)

Spirelf
45 installation
1200
40
1000
35
Duty (GJ/h)

Duty design
as per 800
30
datasheet
600
25

20 400

15 200

10 0
01/11/2014 28/08/2015 23/06/2016 19/04/2017 13/02/2018

Figure 5 Trend of exchanger duty (blue) equipped with Spirelf vs crude flow rate (red) and bottom pumparound flow
rate (green)

44 PTQ Q1 2025 www.digitalrefining.com

petroval.indd 44 09/12/2024 17:25:02

 resulted in a lower coil inlet temperature (CIT) at the fur-
Impact on energy savings and CO2 emissions on heat
nace and extra consumption of fuel to compensate for this
exchangers used in Study B* **
loss of preheat.
The Spirelf vibrating devices were implemented during a With Spirelf
cleaning shutdown, and the performance of the exchangers Gain on energy recovery (Gcal/yr) 14,500
was represented on the same trend. After the installation Gain on energy recovery (TOE/yr) 1,450
Energy savings 872 k€
on 29/11/2015, the average duty was 37 GJ/h, and it was
Gain on CO2 emissions (tons first yr) 4,350
perfectly maintained at this level until 19/04/2018, the date Reduction in CO2 emissions 436 k€
of the turnaround of the unit after 872 days in operation.
Over the entire run with the vibrating devices, the crude Table 5
flow rate was at design value. However, the performance
of the heat exchangers was limited by the regulation of the exchangers (HXs), and the green trend is the crude flow
unit operating on the shell side flow (specifically the bottom of the unit showing operating condition sustainability. The
pumparound flow rate). A few unit upsets occurred, but the trend presented in Figure 7 shows the duty comparison
exchangers were never opened, and performances ben- between the last six HXs (red) and the first six HXs (blue)
efited from occasional unit recirculation, such as October between the two consecutive runs.
2017. • SOR: From the reference run, it was identified that within
The implementation of Spirelf in these heat exchangers six months, the OHTC of the last six HXs (red) dropped to
considerably increased the run length from one year to the level or below the first six HXs (blue), showing the large
two-and-a-half years. Additionally, there was a significant impact of fouling on the performance of the exchangers.
increase in duty, averaging at 25% and equivalent to the The implementation of Fixotal tube inserts to promote
firing of more than 100 tons of fuel gas per month. shear stress in the last three HXs was visible from the SOR,
The savings on fuel consumption over the first year with an OHTC 26% higher than the reference run over the
amounted to 872 k€, and the benefit related to avoided first three months. This was a consequence of the higher
CO2 emissions was in the range of 436 k€, as summarised turbulence generated on the tube side, which is visible in
in Table 5. the duty exchanged in Figure 7, with a +8.3% increase
compared to the reference run.
Case C results • Until chemical cleaning: From the reference run, after
The trend presented in Figure 6 shows a reference run from six months, the performance of the last six HXs contin-
November 2016 to October 2020. From November 2020, ued declining to an OHTC of 200kJ/h.m² °K until a chem-
a new run started, and the OHTC of the six exchangers, ical cleaning (vertical dotted line) was performed in late
including the three equipped with Fixotal (red), was plotted. October 2018 (two years of operation).
The trend in blue is the OHTC of the train’s first six heat The comparison with the Fixotal run showed that the

SOR Nov 2016 SOR Nov 2020

1600.00
600.00

1400.00

500.00
1200.00 Chemical
cleaning
Heat transfer rate KJ/(hr.m2.K)

Chemical
Crude flow shell side (kL/hr)

cleaning
400.00
1000.00
FIXOTAL
installation
800.00
300.00

600.00
200.00

400.00

100.00
200.00

0.00 0.00
6

8/ 7
7

1/ 8
9

1/ 9
9

9 0
/1 20

1 1

4/ 2
2

2
22

3
23
09 201

20 201

28 /201

06 201

16 201

24 201

02 201

1
20 201

29 201

06 /201

14 201

24 202

01 /202

20 202

28 202

06 202

14 /202

24 /202

02 202

10 202

29 202

06 202

15 202
10 /20

10 /20

20

20
1/

2/

2/

3/

6/

4/

2/

2/

3/

6/

8/

1/

2/

5/

9/

2/
5

0
/1

/0

/0

/0

/1

/0

/0

/1

/0

/0

/0

/1

/0

/0

/0

/0

/0

/1

/0

/0

/0

/1

/0

/0

/0

/1
01

18

A-F heat transfer rate kJ/)hr.m2.K) G-L heat transfer rate kJ/)hr.m2.K) CRD charge kL/h Date

Figure 6 Trend of OHTC with Fixotal equipment on half of the exchangers (red) Study C

www.digitalrefining.com PTQ Q1 2025 45

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Q3_OHL.indd 1 05/06/2024 15:02:26
 SOR Nov 2016 SOR Nov 2020
100.00
600.00
90.00

80.00 500.00
Chemical
cleaning
70.00 Chemical

Crude flow shell side (kL/hr)

cleaning
400.00
FIXOTAL
60.00 installation
Duty (GJ/hr)

50.00
300.00

40.00

200.00
30.00

20.00
100.00
10.00

0.00 0.00
16

/0 17

8/ 7
7

/0 18

1/ 9
9

9 0
/1 20

1 1

4/ 2
2

2
22

3
23
28 /201

06 201

16 201

24 201

02 201

20 201

29 201

06 /201

14 201

24 202

01 /202

20 202

28 202

06 202

14 /202

24 /202

02 202

10 202

29 202

06 202

15 202
20

20

10 /20

10 /20

20

20
1/

2/

2/

3/

6/

1/

4/

2/

2/

3/

6/

8/

1/

2/

5/

9/

2/
5

0
/1

/0

/0

/1

/0

/0

/1

/0

/0

/1

/0

/0

/0

/0

/0

/1

/0

/0

/0

/1

/0

/0

/0

/1
01

09

20

18
Duty shell side A-F GJ/hr Duty shell side G-L GJ/hr CRD charge kL/h
Date

Figure 7 Trend of duty with Fixotal equipment on half of the exchangers (red) Study C

OHTC of the last six HXs consistently remained above revealed a significant recovery for both runs. However, the
the OHTC of the first six HXs but declined significantly to reference run still indicated a lower OHTC for the last six
350 kJ/h.m² °K late in September 2022 (period of chemical HXs. In contrast, for the run with the shear stress promoter,
cleaning of the exchangers, vertical dot line) after two years the last six HXs were still producing a significantly higher
of operation. The last six HXs were then delivering +75% OHTC of 990 KJ/h.m² °K in comparison to the reference
OHTC compared to the reference run at the same duration, case at 660 KJ/h.m² °K +50%. This was proof that fouling
even though only the half of the HXs were equipped with on the crude shell side was the limiting factor and that the
the shear stress promoter. chemical cleaning significantly improved the heat transfer
The evaluation of the duty exchanged before the chem- performance of the preheat train. At this stage, a compari-
ical cleaning revealed that 66% of the train’s total duty son of the duty of the complete train reveals a gain with the
was achieved through the last six HXs, compared to only Fixotal of 9% of duty at 96.67 GJ/hr vs 88.5 GJ/hr.
52% during the previous run. The gain in duty before the • End of run (EOR): The comparison of the two runs still
chemical cleaning was in the range of 14% of duty on the shows better heat transfer for the last six HXs when the
complete train, compared to the reference run for the same last three are equipped with the shear stress promoter
run duration. (typically 50% higher than the reference run). After 1,035
Knowing that the shear stress promoter will only influence days of operation, the last six HXs achieved 69% of the
the tube-side fouling rate and heat transfer coefficient, the total duty of the train, which was typically 10% higher than
performance of the last six HXs was impacted significantly the previous run (after the same duration).
by the fouling on the tube side of the first three HXs and the • Average on the complete run: By evaluating the com-
fouling on the crude oil shell side of the six HXs, which was plete run of 1,035 days, the run with the Fixotal inserts
the main contributor to the performance limitation. equipped in the last three exchangers of the preheat train
• From chemical cleaning: Chemical cleanings are typically generated, on average, 34% higher OHTC on the last six
performed after two years of operation, halfway through bundles and a total average increase in duty of 20% on
the four-year turnaround cycle. This cleaning consists of the last six exchangers. Overall, the preheat train with the
light aromatic gasoil recirculation on both tube and shell inserts was generating 3% more duty, equivalent to 56,600
sides to soften the fouling material, followed by steaming GJ over 1,035 days of operation.
to flush and remove part of the fouling material. It is well The energy savings from reducing the firing of the fur-
known that this type of operation does not allow a full nace and, consequently, the reduction in CO2 emissions
recovery of performance, as the older deposits harden and of the plant yielded economic benefits, as summarised in
age, so only mechanical cleaning would be efficient to fully Table 6. This is equivalent to 405 k€ per year, even though
recover heat exchanger performance. some heat transfer limitations were reached.
The evaluation of the OHTC after the chemical cleaning As the residue on the tube side cooled down much faster

www.digitalrefining.com PTQ Q1 2025 47

petroval.indd 47 09/12/2024 17:25:03

 Comparisons
Impact on energy savings and CO2 emissions on heat
Nowadays, many incentives are in place to encourage the
exchangers used in Study C* **
reduction of CO2 emissions at every level, and the industry
With Fixotal sector is one of the largest contributors.5 Refineries and
Gain on energy recovery (Gcal/yr) 4,500 chemical plants are mainly operating with shell and tube
Gain on energy recovery (TOE/yr) 450 heat exchangers for heat recovery. Reducing their CO2
Energy savings 270 k€
emissions can be done right now thanks to these techni-
Gain on CO2 emissions (tons first yr) 1,350
Reduction in CO2 emissions 135 k€ cal solutions, even as longer-term projects are ongoing for
large-scale impacts. These technologies are available and
Table 6 can be retrofitted to any shell and tube exchanger within a
few weeks.
than during the reference run, there was less potential for Comparing the three technologies would be a difficult
heat recovery through the first six HXs. In addition, the exercise, as they are not designed to operate on the same
total crude flow was 8% lower during the run with Fixotal type of feed, the same level of flow conditions, and do not
(due to some unit upsets), which reduced the heat trans- have the same mechanical lifetime. However, whenever it
fer performance as a result of the lower Reynolds number. is possible, and if fouling mitigation is the driving force to
Nevertheless, the unit achieved better overall heat transfer use inserts, priority should be given to selecting the inserts
performance. that provide a mechanical cleaning effect (Turbotal and
Spirelf).
Combined benefits Although there are already a wide range of potential
Significant improvements related to the use of tube inserts applications, exploring benefits in different flow conditions
were highlighted by the three studies presented, and some or with various types of fluids and processes could be very
concluding remarks can be drawn from these field data interesting. Future technological developments could focus
analyses. For applications A and B, the run lengths with the on implementing new technologies for dual-phase flows to
tube inserts were, at minimum, doubled compared to the improve heat transfer at minimum cost on pressure drop.
same run with bare tubes without any modifications of the
heat exchanger tubes. Nomenclature
In Study C, the operator is constrained by regulation to HXs Heat exchangers
shut down and inspect the whole plant every four years. It BWG Tube wall thickness in Birmingham wire gauge
is not possible to target extended run length since a single OD Outside diameter of tube (mm)
chemical cleaning in the middle of the run is sufficient to CIT Coil inlet temperature
recover enough heat transfer capacity. The implementation OHTC Overall heat transfer coefficient kcal/h.m² °C or kJ/h.m² °K
of Fixotal was, therefore, used to optimise heat recovery, SOR Start of run
even though the fouling on shell side was predominant. EOR End of run
In each case, the performances of the heat exchangers TOE Ton of oil equivalent = 10 Gcal
were increased in terms of heat transfer. This improvement
(*) Cost of energy considered €600 per TOE
was translated in OHTC (Study A) with both an increased
(**) Taxes on CO2 emissions = €100 per ton
and a stabilised level of heat transfer over the run.
For Study B, the benefit was directly expressed in duty, References
with an average increase of 25% during the run, signifi- 1 Petitjean E., Aquino B., Polley G.T., 2007, Observations on the Use
cantly reducing the firing of the downstream furnace by of Tube Inserts to Suppress Fouling in Heat Exchangers, Hydrocarbon
about 100 tons of gas per month. For study C, the increase World 2007, Ed. Touch Briefings, pp47-51.
of OHTC with only three HXs equipped with Fixotal out of 2 Bories M., Patureaux T., 2003, Preheat train crude distillation foul-
12 unbalanced the preheat train performance and allowed ing propensity evaluation by Ebert and Panchal model, Proc. Heat
an increase in duty and heat recovery even though the Exchanger Fouling & Cleaning: Fundamentals & Applications, Santa
operating conditions were unfavourable compared to the Fe, July 2003.
reference run. 3 Pouponnot F., Krueger A. W., 2004, Heat Transfer Enhancement
The benefits achieved in the three applications demon- and fouling mitigation by heat exchanger tube inserts, Int Conf. On
strate the potential improvements achievable with stand- Heavy Organic Depositions, Los Cabos, Mexico.
ard shell and tubes heat exchangers when limitations come 4 Aquino B., Derouin C., Polley G.T., 2007, Towards an understanding
from either tube side or shell side film coefficient or from of how tube inserts mitigate fouling in heat exchangers, Int Conf on
fouling deposition in either tube or shell side. The complete Heat Exchanger fouling and Cleaning, Tomar, Portugal.
range of operation must then be evaluated to highlight 5. Aubin N., Joung J., 2023, Quick win on carbon footprint by improv-
the main contributors to the thermal resistances of the ing existing assets, AFPM 2023 Summit, Dallas, Tx, USA.
exchangers and assess if these limitations can be tackled
with these inserts. This must be done by comparing the Nicolas Aubin is Technical and R&D Manager at Petroval, based in
effect of tube inserts with bare tubes at different levels of Saint-Romain-de-Colbosc, France. He has 20 years of experience and
throughput, but also taking into account the level of fouling holds a master’s in chemical engineering.
typically reached in these flow conditions at SOR and EOR. Email: n.aubin@petroval.com

48 PTQ Q1 2025 www.digitalrefining.com

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 Overcoming the complexities of
spent caustic treating
Case studies focus on sustainable solutions for treating highly alkaline spent caustic
refinery waste with widely available carbon dioxide

Vilas G Gaikar, K V Seshadri and Vaibhav B Kamble

Institute of Chemical Technology

S
ulphur compounds such as mercaptans, thiols, and caustic are challenging. It is one of the most problematic
thiophenols are usually first removed in the sweet- industrial wastes in terms of disposal because it is difficult
ening process from petroleum products by extraction to deal with by biological treatment and wet air oxidation.
using aqueous alkaline solutions, which generates caustic Phenols, beyond specific concentrations, are highly inhibit-
waste. The sulphidic spent caustic comes from scrubbing ing compounds in the metabolism of micro-organisms.
of liquefied petroleum gas (LPG) and pentane from a fluid The naphthenate salts may result in excessive foaming
catalytic cracker (FCC) and crude distillation unit (CDU). and/or emulsification of a substantial amount of the oil
Naphthenic spent caustic comes from the treatment of phase. The physical separation of disulphides from the
kerosene, diesel, and jet fuels, while cresylic spent caus- alkaline aqueous stream is poor because of an exceedingly
tic comes from the treatment of vis-breaker gasoline. The small difference in the densities of the two phases. For
major volume of the spent caustic is produced in the treat- example, di-methyl-disulphide, di-ethyl-disulphide, and
ment of kerosene. The multiple spent caustic streams from ethyl-propyl-disulphide have specific gravities of 1.057,
different units finally add up to a mixed spent caustic that 0.992, and 0.964, respectively.3
holds sulphidic, naphthenic, and cresylic compounds at Thus, aqueous solutions tend to carry some colloidal oil
significantly high concentrations. The undissolved organics phase (1-2%) in a finely dispersed form, contributing sub-
and/or grease may also appear in the spent caustic because stantially to higher values of COD of the waste stream. The
of incomplete phase separation in the earlier processes. toxic components of the spent caustic must be reduced
Catalytic mercaptan Merox oxidation technology, used before the effluent can be subjected to conventional treat-
globally, is based on a special UOP catalyst to accelerate ment facilities, and the cost of the pretreatment depends on
the oxidation of mercaptans to disulphides at optimum the nature of the impurities. If these compounds are recov-
operating conditions in an alkaline environment. The disul- ered by some physical means with/without chemical treat-
phides usually form a separate oil phase from the remain- ment, it would bring down the impact of these compounds
ing aqueous alkaline solution, and the separated caustic is on the environment and ease the treatment of residual COD
recycled to the reactive extraction operation. in conventional biological waste treatment plants.
Between the extraction and oxidative regeneration cycles, The neutralisation of free alkali by a mineral acid to drop
the concentration of sodium hydroxide (NaOH) depletes as the pH of the spent caustic is a straightforward choice.
it reacts while components with stubborn resistance to oxi- However, deep neutralisation to pH level <3 generates a
dation, such as phenols and cresols (as sodium salts), emul- large volume of mal-odoriferous gases containing hydro-
sified naphthenates, and catalyst residuals, accumulate gen sulphide (H2S) and volatile mercaptans, which must
along with inorganic sulphides, thiosulphates, carbonates, be treated in an auxiliary unit that generates a secondary
and Fe+2 precipitates, needing frequent purge.1 aqueous waste.
These spent caustic waste solutions usually have a large Selection of the appropriate metallurgy is also required to
free alkalinity (caustic concentration in the range of 2-15% protect the equipment from severe corrosion at low pH con-
with pH~13) with appreciable concentrations of sulphides, ditions. Restricting the pH above 8.0 can avoid the forma-
phenols, mercaptans, amines, naphthenic acids, and/or tion of acidic gases. Waste incineration is rarely employed
other acidic organic compounds. The chemical oxygen because of its high energy consumption and the release of
demand (COD) values of the spent caustic effluent exceed hazardous compounds such as furans and dioxins. Wet air
100,000, particularly those with cresylic and naphthenic oxidation (WAO) of phenols requires a minimum tempera-
acids. In a few cases, as much as 3% phenolic content has ture of 200ºC.
been seen in the spent caustic.2,3 High-temperature WAO at 240-260°C can oxidise all
phenols and reduce the COD, producing a biodegradable
Spent caustic treating effluent. To reduce the formation of copious amounts of
The complexities of processes involved in treating the spent ferrous iron sludge in the Fenton oxidation process, new

www.digitalrefining.com PTQ Q1 2025 51

ICT.indd 51 10/12/2024 10:38:17

 PG: Pressure gauge
PG
NV MFC: Mass flow controller
CO2
pH: pH meter
V V TI: Temperature indicator
C100 P: Pump
PG V: Vessel
1500mm PSV: Pressure safety valve
V random NV: Non-return valve
packing V: Valve
PG pH
V200
TI

V100
V20
P200

V300 Oil phase

P100
CO2 cylinder
Aq. phase to
waste treatment

Figure 1 Schematic for treating spent caustic with CO2

homogeneous and heterogeneous catalysts have been rec- turbine agitator running at 1,500 rpm and a flow meter to
ommended. However, the process works to its best under measure the amount of CO2 sparged just below the impel-
acidic conditions, and neutralising caustic still becomes a ler. The exit gaseous stream from the stirred vessel was
prerequisite.4 connected to a packed column with a provision for spraying
an alkali solution (1% w/v) to chemically absorb any acidic
Treating oxidation-resistant compounds gases that might be liberated in the reaction or stripped off
In our quest for developing sustainable solutions to envi- from the solution by CO2. Additionally, residual CO2 in the
ronmental issues of petroleum refining, in the current work, exit gas reacts with alkali in this column. For comparison,
as a sustainable approach for treating spent caustic, the the spent caustic waste was also neutralised using mineral
use of carbon dioxide (CO2) is proposed if the major compo- acids with continuous pH monitoring, initially to a neutral
nents of the spent caustic are oxidation-resistant phenolic pH and then to a pH below 3.
or cresylic compounds.
CO2 is widely available as a waste gaseous stream in Results
manufacturing industries and petroleum refining. CO2 Since it was not possible to identify each chemical compo-
reacts with the excess alkali of the spent caustic effluent in nent in the effluent, the COD was used as a monitoring var-
an acid-base reaction, forming sodium carbonate (Na2CO3) iable. The pH of the spent caustic effluent from Refinery #1
and reducing the pH below 9. Being more acidic than phe- was 12.9 with a COD of 40,600 ± 200 mg/L, while values
nolic compounds, CO2 reacts further with the alkali metal were 12.4 and 44,500 ± 200 for the effluent from Refinery
salts of phenols and/or thiols. Thiophenol (pKa~6.7) salts #2. During the first phase of pH reduction to 10, when CO2
may not react completely, while naphthenate salts will not reacts with excess alkali in reaction (R1), no COD reduction
react at all with CO2. was seen:
The phenol(s) and thiols, generated in the neutralisation
reaction, separate as an oil phase from the spent caustic. 2NaOH +CO2  Na2CO3+H2O (R1)
Surprisingly, no neutralisation of alkaline streams with
CO2 is practised in refineries, although the use of CO2 for Thereafter, CO2 reacts with sodium phenates, forming
the pH adjustment of spent caustic before WAO has been Na2CO3 + sodium hydrogencarbonate (NaHCO3), releasing
suggested.5 The pH adjustment was limited to 10, which phenol(s) as a separate oil phase and reducing the pH of
was not enough to separate phenolic compounds from the the effluent below 9. Thiols can also react similarly:
spent caustic.
For recovery of phenols, the pH must be brought at least 2Ph-ONa + 2CO2  2PhOH + Na2CO3 (R2a)
one unit below the pKas of cresols/phenols. The treatment
of Merox unit spent caustic with CO2 gave a 65% COD Na2CO₃+H2O+ CO2  2NaHCO3 (R2b)
reduction when the pH decreased below 9.0, while the sec-
ond stage of solvent extraction gave an overall 90+% COD After a first slow decrease in the COD, with the addi-
reduction. The process is controlled by the kinetics of mass tion of CO2, there was a sharp drop in the COD, indicating
transfer of CO2 into aqueous solution. separation of the organics from the aqueous solution (see
Figure 1 shows a schematic of a laboratory setup consist- Figure 2). The final CO2-treated effluent from the stirred
ing of a stirred vessel equipped with a six-blade Rushton vessel was an emulsion of the oil phase with the aqueous

52 PTQ Q1 2025 www.digitalrefining.com

ICT.indd 52 10/12/2024 10:38:17

 www.zwick-armaturen.de

Q3_Zwick.indd 1 05/06/2024 15:07:50

 effluent that was sent to a phase separator where it sep-
arated into two phases: an oil phase of mostly phenolic
50000
compounds and another aqueous phase having residual 45000
organic pollutants and Na2CO3. 40000
Due to high viscosity and densities close to that of the

COD (mg/L)
35000
aqueous solution, the oil droplets do not coalesce easily. 30000
The oil phase separated from the spent caustic of Refinery 25000
#1 after the treatment with CO2 had a density of 0.98 and 20000

viscosity of 25.9 mPa.s. It took more than 72 hours to get 15000

10000
two clear, distinct phases on standing. The residual COD of
5000
the aqueous solution at pH <9 was 12,980 ± 1,340 mg/L.
0
About 1.8% of oil by weight separated from the aqueous 0 50 100 150 200 250
solutions, giving a 70% reduction in the COD. The sample CO2 (mg/L)
from Refinery #2 also showed a 67% reduction in COD
after treatment with CO2. Figure 2 Reduction in COD of spent caustic waste by
Due to the acid-base type of reaction of CO2 with alkali, treatment with CO2 (ο: Refinery #1, : Refinery #2).
no free CO2 is expected to exist in the solution. The sol-
ubility of CO2 in water is 2.03 x 10-3 gmol/L at 30ºC. For Treatment with activated carbon
an agitated stirred vessel, the mass transfer coefficient
and hold-up were estimated as 0.36 1/s, and 3.0 ± 0.5%, Activated carbon Residual Adsorbed COD
Sr. no (wt%) CO (mg/L) (mg/L)/gm
respectively, from the following correlations:6
0 4,030 -
1 0.5 2,221±33 362±7
2 1.0 1,977±91 205±9
(1) 3 1.5 1,757±41 152±3

and Table 1

(2) COD reduction
A substantial decrease in the COD of the aqueous phase
The estimated mass transfer rate of CO2 into the aqueous was seen after the toluene extraction. Figure 3 shows that
caustic solution is 7.4 X 10-4 gmol/L/s and is controlled by more than 60% of residual COD was transferred to toluene
the hydrodynamic conditions and poor solubility of CO2. Not in a single stage. The COD of the CO2-treated spent caustic
all the CO2 that is sparged into the reactor reacts. Therefore, reduced from 12,540 to less than 5,100 mg/L even with
to react in the once-through operation, suitable mass trans- 10% (v/v) of toluene used for the extraction. With equal
fer equipment, such as a stirrer vessel with a gas-inducing volume of toluene, the COD reduced further to 4,030 ± 100
impeller, will be necessary for the complete utilisation of CO2. mg/L.
Since the oil phase mostly consists of compounds of Table 1 shows another 50% reduction of COD after the
phenolic/cresylic nature, toluene was added in the second adsorption on activated carbon activated the carbon at dif-
step of treatment to dissolve the oil phase and even extract ferent loadings in a single-stage operation, as a polishing
phenols from the aqueous phase. Paraffinic solvents do stage.
not dissolve phenolic compounds well. The toluene extract The spent caustic, treated with CO2 at Refinery #2 at
can be sent for recovery of phenols by physical methods or 600 L scale, showed a higher value of COD (28,400 mg/L)
recycled back to the refinery for blending with a suitable and pH 9.42, indicating that the CO2 treatment was not
stream. complete. It was directly treated with activated carbon

70 8
% transfer of COD to toluene

7
68
Partition coefficient

6
66
5
64 4
3
62
2
60
1

58 0
0 0.5 1 1.5 3000 3500 4000 4500 5000 5500
Vorg /Vaq COD of aqueous phase (mg/L)

Figure 3 (left) % transfer of organics to toluene (right) Partition coefficient of organics towards toluene in terms of COD

54 PTQ Q1 2025 www.digitalrefining.com

ICT.indd 54 10/12/2024 10:38:17

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 The cost of WAO depends on the operating conditions,
1 which are related to the COD of the effluent. More severe
1% w/v operating conditions are needed to treat effluent with
0.95 2% w/v
3% w/v higher values of COD. Higher-strength waste streams are
0.9 frequently diluted to bring COD below 50,000 for better
efficiency of the WAO process. The carbonation can eas-
C/Co

0.85
ily manage even a larger COD-containing spent caustic
0.8 stream.
The stronger the organic content of spent caustic,
0.75
whether phenolic or cresylic acids, the more economical
0.7 it is, as more recovery of phenols in the form of organic
0 2 4 6 8 10 12 material is possible. If required, the waste stream from the
Time (min)
carbonation operation, with or without a solvent extraction
step, can be fed to the WAO unit to oxidise residual organic
Figure 4 Kinetics of adsorption of COD on activated carbon and inorganic sulphides in slightly alkaline conditions to
at different loadings sulphates, which can be run at milder conditions of 100ºC.
Since the pH is not brought below 8.5, there was no evo-
without the intermediate solvent extraction step. Figure lution of malodorous sulphide gases, which is common if
4 shows the kinetics of the adsorption for three different the pH of spent caustic is brought down by the addition
loadings of activated carbon. At 1% w/v loading, the acti- of strong mineral acids. The carbonation process, however,
vated carbon was able to pick up almost 8,560 COD/gm does not touch inorganic sulphides, thiophenols and naph-
of carbon. The exponential decay of COD with time shows thenates in the solution. Deep acidification of the spent
that the process is of first order and controlled by the exter- caustic releases phenols (at pH <9), thiophenols (at pH
nal mass transfer of organics to the solid adsorbent surface. <6.0), and naphthenic acids at (pH <4). However, the acid-
One of the major concerns in the treatment of spent caus- gas absorption system was overloaded with the release of
tic waste is the nature of compounds, mostly phenolic and copious amounts of H2S and mercaptans gases, generating
thiophenols, which could be refractory to the usual biologi- a secondary waste. The mineral acid addition rate must,
cal treatment. The UV spectra of the spent caustic from two therefore, be adjusted appropriately to ensure a managea-
refineries show strong absorbance peaks at 275 nm and ble rate of gas release in the neutralisation reactor, a factor
240 nm corresponding to phenols/cresols and thiophenols, often not discussed during deep acidification.
respectively. After the treatment with CO2 and toluene, the
effluent shows a substantial reduction in absorbance in the Ionic liquid treatment
UV region. The main limitation of the carbonation process is the slower
Thus, the process definitely removes the phenolic com- rate of CO2 transfer into the aqueous solution. If the CO2
pounds, and the residual solution becomes amenable to available is a pure gas, a gas-inducing impeller can be
biological treatment before the water can be released to the used in the stirred vessel to use it completely in the reactor.
environment. After the activated carbon treatment, there Operating costs can be significantly reduced if CO2 is avail-
was negligible absorbance at these wavelengths, showing able at the site as an effluent stream from any manufactur-
complete removal of biologically refractory compounds. ing facility or even when mixed with other gases.
Sabri et al7 reported an extremely high removal of COD
Comparative results (99.8%) by treatment of spent caustic with ionic liquids
It will be worthwhile to compare the results of carbonation (ILs). At high pH values, all organics are in ionic form,
and solvent extraction with the well-established WAO for preventing their extraction into organic solvent. So, direct
treating the spent caustic effluent. The carbonation works solvent extraction without pH adjustment at pH of 12.9 is
at ambient conditions of temperature and pressure. It thus unlikely to recover any of the phenolic/cresylic compounds
would not require large capital investments and operating into an organic solvent. The acidification enables the con-
costs, while WAO needs temperatures of 200ºC and 27.5 version of ionic species to their non-ionic form.
bar to 260ºC and 86 bar pressures and thus high-pressure At pH below 9, all the phenolic compounds must be
equipment. WAO destroys the organics, adding them to the in molecular form to allow their complete extraction.
environmental load as gaseous CO2. In contrast, the car- Considering that COD-contributing organic compounds are
bonation process uses CO2 and recovers the phenolics and strongly ionic at alkaline pH conditions, ion exchange with
cresylics as a separate oil phase. This may become more ILs cannot be ruled out. However, the work did not disclose
economical when recovering these high-value compounds the physicochemical processes involved nor the regenera-
from spent caustics with significant amounts of compounds. tion of the IL phase. Considering the prohibitively excessive
A typical WAO, in industrial conditions, gives about an cost of ILs, their application in the recovery of phenolics
80% reduction in COD in about 45-120 minutes, while from spent caustic is not practical unless efficient regener-
the first stage of the proposed carbonation process alone ation and recycling methodologies are developed to reduce
brings down the COD by 65-70%. In the two-stage pro- the IL cost per unit of treated spent caustic to economically
cess, the COD reduction was 90+%. workable levels.

56 PTQ Q1 2025 www.digitalrefining.com

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 ILs tend to have high viscosities at ambient tempera- level, demanding a secondary treatment unit for the cap-
tures, which can limit mass transfer rates, although the ture of H2S.
high removal efficiencies result from a large mass transfer In refineries, the spent caustic stream is mixed with other
driving force. The adsorption of organics from spent caustic aqueous solutions, diluting the spent caustic effluent. If the
solutions on bleaching earth, alumina, and petroleum coke spent caustic from the kerosene treatment unit, with its
has been reported under alkaline conditions.3 remarkably high load of phenolics, is treated directly with
Bleaching earth could reduce COD values by 60%, prob- CO2, the process may provide an economic incentive to
ably by ion exchange and/or intercalation of the organic ani- recover phenols as a valuable product.
ons between layered structures. However, alumina-based We believe that using a CO2 waste stream to treat another
adsorbent reacted chemically with alkali, resulting in adsor- waste solution is a sustainable solution. Such positive solu-
bent bed collapse in the column. tions can have a positive and profitable effect across the
With petroleum coke, there was no removal of COD com- entire spectrum of the oil industry.
ponents from the spent caustic. Instead, the spent caustic
desorbed other organic compounds, increasing the COD References
values. It is not surprising due to the ionic nature of organic 1 Pino-Cortés, E., Montalvo, S., Huiliñir, C., Cubillos, F., Gacitúa,
compounds under strongly alkaline conditions. The result- J., (2020) Characteristics and Treatment of Wastewater from the
ing contribution to the COD does not allow their adsorption Mercaptan Oxidation Process: A Comprehensive Review, Processes,
on coke. When pH is reduced and phenolic compounds are 8, 425; doi:10.3390/pr8040425.
converted into a molecular form in the present studies, their 2 Rita, A.I., Rodrigues, C.S.D. Santos, M. Sanches, S. Madeira, L.M.,
adsorption on activated carbon improves significantly. (2020) Comparison of different strategies to treat challenging refin-
ery spent caustic effluents, Sepn. Purifn. Technol., 253, 117482-97,
https://doi.org/10.1016/j.seppur.2020.117482.
Conclusion
3 Czimer, B., Kovács, A., Petró, J., (2015) Treatment of Spent Merox
The treatment of highly alkaline waste streams using CO2
Caustic Waste in Industrial Ecology Frames, Period. Polytech. Chem.
provides a sustainable solution. The phenolic compounds
Eng., 59(3), 215-220, DOI: 10.3311/PPch.7601).
are removed by bringing the pH of the solution below pKas
4 Roudsari, M. H., Soltani, M., Seyedin, S. H., Chen, P., (2017)
of phenol(s) and efficiently separating the oil phase. (In
Investigation on New Method of Spent Caustic Treatment, J. Multidisc.
molecular form, phenol and cresylic acids have poor solu-
Eng. Sci. Technol., 4(6), 7459-7464.
bility in water). 5 Kumfer, B.J., Felch, C.L., Brandenburg, B., Ishmann, R.R., (2014), US
The phase separation needs to be improved by a solvent patent, 8,734,648 B2, Siemens Energy, Inc., Orlando, FL (US).
extraction step, using an organic solvent that can dissolve 6 Doble, M., Kruthiventi, A. K., Gaikar, V.G., (2004) Biotransformation’s
the separated phenolic oil. However, neutralisation by and bioprocesses, Marcel Dekker, New York.
CO2 is restricted to free alkali and alkali salts of phenols. 7 Sabri, M.A., Ibrahim, T.H., Khamis, M.I., Nancarrow, P., Hassan, M.F.,
Thiophenols and all naphthenic acid(s) remain in the solu- (2018) Spent caustic treatment using hydrophobic room temperatures
tion because of their stronger acidic nature. ionic liquids, J. Ind. Eng. Chem., 65, 325–333, https://doi.org/10.1016/j.
The limitation of slower solubilisation of CO2 due to its jiec.2018.05.002.
poor solubility in water can be overcome using a suitable
unit to increase mass transfer area between gas and liq- Dr Vilas G Gaikar is Bharat Petroleum Chair Professor.
uid phases, allowing maximum CO₂ use in the process. It is Email: vg.gaikar@ictmumbai.edu.in
also possible to use gaseous effluent from thermal energy K V Seshadri is Adjunct Professor in the Department of Chemical
plants or refineries, having CO₂, nitrogen (N₂), nitrogen Engineering at the Institute of Chemical Technology, Matunga,
oxide (NOx) and sulphur dioxide (SOx), depending on fuel Mumbai-400019, India.
type. However, if SOx and NOx are present, they will react Vaibhav B Kamble is a post-graduate student in the Department
faster than CO₂ and further reduce the pH. The risk of H2S of Chemical Engineering at the Institute of Chemical Technology,
evolution remains in such a case if pH drops to an acidic Matunga, Mumbai-400019, India.

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merichem.indd 1 10/12/2024 10:06:24
 Revamping sulphur recovery units
with high-level oxygen enrichment
Two case studies demonstrate how high-level oxygen enrichment can address two
distinct issues that existing SRUs are likely to face in the future of refining

Debopam Chaudhuri, Theresa Flood, Denny Li, and Jyoti Bist

Fluor

A
ll crude oil contains some sulphur compounds. Reaction 1 is highly exothermic, while Reaction 2 is
These compounds range from the simplest form, endothermic, with a net effect of exothermicity for the net
namely hydrogen sulphide (H₂S) found in natural conversion described by Reaction 3. Another reaction of
gas, through simple mercaptans compounds (R-S-H) to importance and of special interest to this discussion is the
very complex molecules. These sulphur compounds pass destruction of ammonia in the presence of air:
through to the various distillate products in various degrees
of concentration. If allowed to remain in the distillates, they 2 NH₃ + O₂ → 3/₂ N₂ + 3 H₂O
have adverse effects on the environment, are corrosive to
equipment, and deactivate high-value catalysts of down- The Claus reaction furnace needs to be hot enough to
stream processes. Therefore, sulphur treatment and recov- ensure near-complete destruction of ammonia to nitrogen,
ery become inevitable. with the target typically 1,260°C (2,300°F) for a standard
The sulphur compounds present in the crude get dis- Claus.
placed from the hydrocarbon phase as H₂S. This H₂S is Traditional sulphur plants employing the modified Claus
either captured by an amine solvent in the amine treatment process utilise air as the source of oxygen in the thermal
units or dissolved in the process condensate. The amine cir- reaction furnace. The major drawback of using air as the oxy-
culates in the refinery in a closed circuit, capturing the H₂S gen source is the large amount of nitrogen that comes with
from the hydrocarbon phase in various amine treaters. This the oxygen supply. The nitrogen from air adds to the hydrau-
‘rich’ amine (rich in H₂S) is then regenerated in the amine lic load of the unit, thus ‘eating up’ capacity. The nitrogen also
regeneration unit (ARU) to liberate the H₂S gas and regen- adds thermal inertia, lowering furnace temperatures and
erate lean amine (lean in H₂S) to be circulated back to the increasing the duties of sulphur condensers and reheaters.
various amine treaters. Oxygen enrichment has been implemented in many sul-
Similarly, the sour water generated from the various pro- phur plants to debottleneck the process and reclaim SRU
cess units in the refinery is treated in sour water stripping capacity. Oxygen enrichment is the process where part
unit(s) (SWSU) to liberate the H₂S and other gases. The or all of the oxygen needed for the modified Claus reac-
combined stream of the H₂S-rich gases from the ARU and tion is replaced by pure oxygen. Conventionally, oxygen
SWSU is then sent to the sulphur recovery unit (SRU).
Figure 1 demonstrates how sulphur travels through the
various process units and hydrocarbon in a refinery, start- Light ends
ing from the crude oil until recovered as elemental sulphur. treatment Amine
regen.
The H₂S in acid gas streams is converted to elemental unit
sulphur utilising the modified Claus process. The typical Light & mid
distillate
feed gas streams to an SRU, originating from the amine treatment
Sulphur
regeneration and the SWSUs, contain varying amounts Crude
recovery
distillation
of H₂S as the sulphur source. The process involves burn- unit
Heavies
ing the acid feed gas with a sub-stoichiometric amount of treatment
air, typically just enough to combust approximately a third Sour
water Sulphur
of the H₂S to SO₂. The SO₂ formed then reacts with the stripper
unconverted H₂S to produce elemental sulphur. unit
The main reactions involved are:
Sulphur in oil Sulphur in water
(1) Sulphur in amine Sulphur in gas
H₂S + /₂ O2 → SO2+H2O + Heat
3

2 H₂S + SO₂ ↔ 3 S + 2 H₂O – Heat (2)

3 H₂S + 3/₂ O₂ → 3 S + 3 H₂O + Heat (3) Figure 1 Simplified sulphur map of refinery

www.digitalrefining.com PTQ Q1 2025 59

FLUOR.indd 59 10/12/2024 10:45:48

 feed gas composition is the same for both the base case (air
Feed gas composition only operation) and the revamp case (oxygen enrichment)
ARU acid gas SWSU acid gas operations. The only differential between the two cases for
Component Mol% Mol% the feed gas is quantity.
H₂S 93.5% 38.0% Table 2 provides a summary of the flow rates for the var-
NH₃ 0.0% 38.0% ious streams marked in the simplified flow diagram shown
H₂O 4.5% 22.0% in Figure 1 for the two operating cases: base case – air only
Balance 2.0% 0.0% operation; revamp case – oxygen enrichment.
Total 100.0% 100.0% As Table 2 clearly shows, when the unit operates with
oxygen enrichment and processes 150% of the base plant
Table 1 capacity, the process gas flow from the first sulphur con-
denser is still less than the base case. Hence, there is no
enrichment is classified as low-level, mid-level, and high- impact on the hydraulic load of the unit downstream of the
level. This corresponds to the amount of pure oxygen mixed first sulphur condenser even while it processes more acid
into the air-oxygen mixture sent to the furnace. Low-level gas.
oxygen enrichment typically limits the overall oxygen con- The primary drawback of implementing high-level oxy-
centration to 28 vol% O₂ in the final mixture of air and gen enrichment is that with so little nitrogen diluent in the
oxygen, whereas high-level oxygen enrichment involves furnace, the bulk gas temperature achieved via combustion
a concentration greater than 45 vol% O₂. The in-between exceeds the allowable limits for any available refractory.
concentration is categorised as mid-level enrichment. Hence, special design modifications are needed to provide
adequate temperature control in the furnace.
Case study 1: Capacity enhancement Typically, the major equipment that is either replaced or
The first case study involves a sulphur plant consisting of newly installed in the revamp of an existing SRU includes
three identical trains designed to process refinery acid gas the COPEII ejector, the COPEII burner, the AAG preheater
equivalent to a total of 450 MTPD (3 x 150 MTPD) of sul- (if the existing one is insufficient), and the first sulphur con-
phur production. The existing SRU consisted of the follow- denser. For this particular revamp, additional updates were
ing systems: required to the existing equipment and piping to accommo-
 Three identical Claus sulphur recovery sections, includ- date increased sulphur production capacity.
ing the thermal and catalytic stages. The specially designed COPE burner allows for the safe
v Dedicated sulphur pit and ejector for each SRU train. and effective processing of separate feed streams, includ-
w A common tail-gas incinerator for all three trains. ing air, high-purity oxygen, acid gases, start-up fuel gas
The refinery needed to increase its sulphur handling capa- and, when necessary, recycle gas.
bility to meet the present and future crude operating trends, The COPEII ejector is a key component in the system
as well as to increase its overall flexibility of operation. The that moderates the furnace temperature. It sends a recy-
owner proceeded to implement Fluor’s proprietary Claus cle stream back to the reaction furnace so that, as more
Oxygen-based Process Expansion (COPEII) high-level oxy- high-purity oxygen is added, the operating temperature
gen enrichment to increase the sulphur handling capability does not rise above the design limit of the furnace refrac-
by 50%. This technology would increase the amount of acid tory. The recycle gas is taken from the outlet of the first
gas equivalent each Claus train can process to 225 MTPD sulphur condenser. The flow of recycle gas is controlled to
of sulphur production while maintaining the same sulphur maintain the desired temperature in the reaction furnace.
recovery efficiency. Oxygen enrichment reduces the vol- The following section provides a detailed description of
umetric flow of process gas and tail gas by reducing the the process and the design modifications implemented in
quantity of nitrogen that enters with the combustion air. the existing unit. The associated design for this case study
This reduction in volumetric flow rate allows for a corre- has been defined in Figure 2. This shows the simplified
sponding increase in SRU acid gas feed rate and a subse- sketch of the front-end section of the SRU through the
quent increase in sulphur production with the same main first sulphur condenser. The items highlighted in red are
equipment in the SRU downstream of the Claus furnace. the equipment or equipment sections that are part of the
The typical composition of the feed gases to the Claus revamp (addition of new equipment and replacement or
section for the sulphur plant is summarised in Table 1. The modification of existing equipment).

Simplified material balance table

Flow rate in kmol/h
Amine SWS Oxygen Process Claus Recycle Process gas
acid gas acid gas air furnace outlet gas from 1st cond.
Stream No. 1 2 3 4 5 6 7
Base case 183 67 0 558 764 0 742
Revamp case 286 67 136 137 800 152 648

Table 2

60 PTQ Q1 2025 www.digitalrefining.com

FLUOR.indd 60 10/12/2024 10:45:48

 LP steam
FC Acid gas
preheater Combustion
AAG
AAG 1 KOD
control
FC

Cond LP steam

FC
COPE
SWS To 1st
ejector 7 preheater
SWS AG 2 AG FC
KOD
6

FC
Claus Waste
O2 3 Burner
furnace heat 5
boiler

FC
1st sulphur Liquid
Air 4 condenser Sulphur

Figure 2 Simplified block flow diagram for Case 1

COPEII operation enhancements further modification of the existing design is needed typi-
The amine acid feed gas (AAG) and sour water acid gas cally in the rest of the unit.
first pass through respective, existing knock-out drums A new first sulphur condenser is required in this case to
to remove entrained liquid droplets before mixing. These provide the necessary duty for processing 225 MTPD of
gases are water-saturated and, when mixed, create the sulphur capacity and to manage the higher flow rate of the
potential for condensation and salt formation. An AAG gas process gas, which now includes the COPEII recycle gas.
preheater is added in the design before the mixing point Additionally, a few modifications in the existing WHB are
to preheat the AAG to achieve an outlet temperature of needed. The expected outlet temperature during oxygen
180°C, using MP steam supplied from Claus waste heat enrichment is higher than the original outlet design tem-
boiler (WHB), avoiding condensation in the mixed stream perature. The proposed modification is to add a new layer
and preventing potential condensation of elemental sul- of castable refractory in the WHB outlet channel. At the
phur when the COPEII recycle gas mixes with the feed acid same time, the piping from the WHB to the first sulphur
gas. After mixing, the three combined gas streams are fed condenser is replaced with stainless steel piping.
to the new, high-intensity COPEII main burner. Condensed sulphur from all sulphur condensers gravity
The main burner ensures high-intensity mixing, a suf- drains through the existing sulphur seal pots and to the sul-
ficiently high combustion temperature, and adequate phur pit. A new pit vent ejector, which sends the vent gases
residence time. The total O₂ required for combustion is sup- from the sulphur pit to the existing incinerator, is needed.
plied by the combination of pure oxygen and air from the The new ejector will be designed for the new unit design
combustion air blower. For this design, the normal oxygen rate of elemental sulphur and higher amounts of devolving
enrichment level at design sulphur capacity is about 55%. gases.
COPEII operation allows for higher levels of oxygen
enrichment without exceeding the temperature limits of Case study 1 summary
the standard refractory linings by recycling process gas For high levels of oxygen enrichment, the COPEII process
from the outlet of the first sulphur condenser to the COPE offers several advantages. The key features of the process
burner. The recycle gas flow rate is controlled to moderate include:
the reaction furnace operating temperature. The expected u Proven technology with demonstrated operation of high
temperature achieved in the reaction furnace is about levels of oxygen enrichment.
1,450°C during oxygen enrichment operation in this design. v Simple process equipment layout and straightforward
The recycle gas is routed to the burner using a new process control.
steam-driven COPE ejector. The recycle gas in COPEII w High level of reliability and flexibility. The process pro-
operation is relatively cool and mostly inert. It acts as a heat vides the benefit of online recycling for normal high-level
sink that absorbs the required amount of the combustion oxygen-enrichment operation and irregular operations such
heat release to maintain the reaction furnace temperature as start-ups, shutdowns, and feed disturbance rejection.
within design limits during oxygen-enriched operations.
The COPE ejector motive steam is taken from the steam Case study 2: Processing lean gas
produced by the WHB downstream of the superheat coil. The second case study looks at a SRU, which needed to
The balance of the first sulphur condenser outlet gas is process appreciable amounts of lean acid gas (LAG) after
processed normally through the catalytic portion of the a refinery upgrade project. The SRU is a traditional unit
SRU train in a similar fashion to the existing SRU train. No designed for the typical AAG and the sour water stripper

www.digitalrefining.com PTQ Q1 2025 61

FLUOR.indd 61 10/12/2024 10:45:48

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 To other plants

FC
SWS
SWS AG AG 3
KOD Preheater
LP steam
AAG
1
AAG FC Cond
KOD Claus Claus
To other plants burner furnace

TGTU 2
Recycle KOD
FC FC

To other plants
4
LAG
LAG FC
KOD
To other plants

O2

Figure 3 Simplified block flow diagram for Case 2

acid gas from the upstream ARU and SWS units. The in the sulphur unit are needed to maintain the furnace tem-
unit has a capacity of 150 MTPD of elemental sulphur perature at an optimum value, above 1,260°C for this oper-
production. ation. To increase the reaction temperature, the following
The refinery has multiple Claus units, each with a dif- design options were considered:
ferent capacity and design. All the individual Claus sec-
tions were designed to operate with a common tail gas Feed preheat
treatment unit (TGTU), with the TGTU recycle gas shared Feed preheat includes heating up the acid gas streams and/
across all of the Claus plants. The feed gas streams were or the air stream supplied to the Claus furnace. Typically,
also shared between the multiple Claus plants. After the low-pressure (LP) steam is used as a heating medium, but
refinery upgrade project, a stream of lean sour gas will also high-pressure (HP) steam (typically the 40-45 barg steam
be processed in the existing sulphur block. A single Claus raised from the WHBs in Claus and Incinerator) can also
unit was chosen to process this additional new LAG stream. be used under more unique cases. The steam level used
Figure 3 presents the configuration of the unit, whereby
the new feed steam of LAG is introduced in the unit. Like
before, the items marked red are the new equipment or The major impact of processing
installations implemented as part of the revamp.
Table 3 lists the feed gas flow rates and compositions for
lean feed gas in the existing Claus
the pre- and post-revamp conditions. The base case data furnace is that it reduces the
for 150 MTPD sulphur production corresponds to the con- reaction temperature due to the
ditions for which the unit had been designed. In general,
the unit operated with lower normal flow rates of AAG.
presence of CO₂ in the LAG
The major impact of processing lean feed gas in the exist-
ing Claus furnace is that it reduces the reaction tempera-
ture due to the presence of CO₂ in the LAG. In this case, the defines the extent to which the streams can be preheated.
amount of LAG is considerable, leading to high amounts of With LP steam, it is limited to 120-130°C, while with 45
CO₂ in the combined feed stream. Hence, the equilibrium barg steam, preheating up to 230°C can be achieved.
Claus furnace temperature is very low. The furnace temper- Unfortunately, the furnace temperature is only 1,100°C,
ature is expected to be around 1,000°C when the mixture even using 45 barg steam to preheat both the acid gas and
of AAG, SWS, and LAG is processed in the existing unit. the air streams.
Since the amount of elemental sulphur generated in the
unit stays well below its design capacity, there is no need Co-firing
for any modification to the sulphur handling section, and Another method of increasing the furnace temperature is to
the only design modification the unit demands is in pro- implement co-firing of fuel gas on a continuous basis. The
cessing the lean gas. combustion of the hydrocarbons helps increase the furnace
temperature to acceptable limits.
Design options For this unit to achieve a temperature of 1,260°C in the
To manage the lean feed into the unit, design modifications furnace, around 800 kg/h of fuel gas co-firing is required.

www.digitalrefining.com PTQ Q1 2025 63

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 Feed gas composition
Amine Acid
Amine acid gas
Gas TGTU Recycle
TGTU recycle SWS Acid
SWS acid gas
Gas Lean Acid
Lean acid gas
Gas
Component Mol% Mol% Mol% Mol%
H₂S 90.0% 30.0% 33.0% 11.0%
NH₃ 0.0% 0% 33.0% 0.0%
CO₂ 5.0% 65.0% 0.0% 81.0%
H₂O 4.0% 5.0% 33.0% 2.0%
Balance 1.0% 0.0% 1.0% 6.0%
Total 100.0% 100% 100.0% 100.0%

Flow rate kmol/h kmol/h kmol/h kmol/h

Base (design) case 192 14 67 0

Post-revamp 107 17 60 183

Sulphur production

Base (design) case 150 MTPD

Post-revamp 110 MTPD

Table 3

The available fuel gas is a stream of hydrogen-rich gas, and preheating the stream has a positive impact on opti-
with the typical composition shown in Table 4. mising oxygen usage. Table 5 summarises the operating
A major drawback of using co-firing on a permanent basis conditions for the unit post-revamp. Since the refinery has
is that it increases the potential for coke formation. This can oxygen available in situ, not depending on outside suppliers
lead to rapid deactivation of the downstream Claus cata- or new installations for the post-revamp high-level oxygen
lysts and also increases the process gas and tail gas flow enrichment operations made this the most viable option.
rates beyond the design capacity of the unit, with the tail A major advantage of the revamp to process the LAG
gas flow exceeding 130% of the base case design value. using high-level oxygen enrichment is that the usage of
Thus, implementing co-firing would require a much larger high-level oxygen enrichment reduces the overall flow of
revamp than just adding the co-firing. For these reasons, process gas and tail gas in the unit, even when the feed gas
this option was not implemented. flow of the unit increased due to the increased flow of the
LAG. The unit remained hydraulically capable of processing
Oxygen enrichment the feed gas mixture with no major modifications beyond
Oxygen enrichment would elevate the furnace operating the Claus furnace. The tail gas flow for the revamp opera-
temperature by removing diluent gases. To achieve the tion is less than 70% of the base case. Thus, all equipment
required furnace temperature, the optimal oxygen enrich- downstream of the Claus furnace continued to operate at
ment level was found to be 60%. To create the correct com- less than design capacity.
bustion and reaction environment with high-level oxygen The revamp also meant that the unit remained capable
enrichment, a new high-intensity burner would be needed. of handling the original feed gas composition if needed,
Oxygen enrichment became the chosen option for the cli- along with any variation from mixing the rich AAG and the
ent. They also elected to replace the reaction furnace. The LAG streams. The oxygen enrichment level can be easily
replacement of the furnace was not a mandatory change fine-tuned based on the expected feed gas compositions,
but was included as part of the project only because the thus allowing this unit to process a wide range of feed gas
existing furnace is old and prone to a number of age-re- compositions.
lated issues.
The acid gas preheater using LP steam is also included in
the design, as the LAG is colder than ambient temperature, Unit operating conditions

Parameter Value
Fuel gas composition Amine acid gas (kmol/h) 107
SWS gas (kmol/h) 60
Component Amount in Mol%
Lean acid gas (kmol/h) 183
Hydrogen 56
TGTU recycle (kmol/h) 17
Nitrogen 10
Oxygen (kmol/h) 60
Methane 22
Furnace temperature (ºC) >1,260
CO₂ 5
Tail gas flow (% of design) <70
Ethane 5
Sulphur production (% of design) <75
Propane 2

Table 4 Table 5

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 Case study 2 summary
Implementing the high-level oxygen enrichment in this pro-
ject allowed the unit to operate with the revised feed gas
composition. Implementing high-level oxygen enrichment
had the following advantages:
u Minimum revamp needed. Existing equipment (burner
and furnace) replaced in situ. New exchanger added in
available space. No new plot area required.
v Operational flexibility. Unit able to operate over a wide
range of feed gas compositions by managing the level of
oxygen enrichment.
w No impact to the unit beyond the existing Claus furnace.
Operating sulphur handling capacity post-revamp well
below design values.

Takeaways
In conclusion, SRUs across the globe may need to upgrade
to meet future demands. The most common requirement
is the ability to process higher sulphur loads, as refineries
across the globe are processing crudes with higher sulphur
content and implementing residue conversion projects.
Other adaptations are frequently required for processing
more challenging feed ‘cocktails’, which may be encoun-
tered when processing lean acid gas streams.
Oxygen enrichment has proven to be a very successful
engine for managing multiple requirements in SRUs, both
for capacity enhancements and dealing with very chang-
ing acid gas streams, as the case study data proves. These
revamp options provide more efficient and cheaper options
for operations compared to constructing new plants to
cater to their new needs.

COPE and COPEII are marks of Fluor.

Debopam Chaudhuri is a Process Engineer with Fluor Daniel India in

New Delhi and is the Subject Matter Expert and a Fluor Fellow of sul-
phur recovery processes. He has 23 years of experience in petroleum
refining, petrochemical complexes, and upstream projects. Chaudhuri
earned his BSc and BTech degrees in chemistry and chemical engi-
neering from the University of Calcutta.
Theresa Flood is a Process Lead Engineering Director and a Fluor
Fellow for Sulphur Technology. She has 35 years of design experience
in the sulphur recovery, gas processing, power, and petroleum refining
industries. Flood’s sulphur recovery and tail gas treating technology
specialties include modified Claus processes, ammonia destruction
techniques, oxygen enrichment, hydrogenation amine, and SOx
clean-up.
Denny Li is a Principal Process Engineer with 18 years of experience
in designing gasification, syngas, and sulphur technologies. His pro-
ject development experience has ranged from technical and economic
feasibility studies, process design packages, and front-end design
through commissioning activities. Li has extensive experience in
developing process simulations for syngas, gas treatment, and sulphur
technologies.
Jyoti Bist is a Process Engineer with Fluor Daniel India in New Delhi.
She has 13 years of experience in FEED and detailed engineering pro-
jects in petroleum refining and petrochemical complexes. Bist earned
her BTech degrees in Applied Petroleum from University of Petroleum
and Energy Studies, Dehradun.

www.digitalrefining.com

FLUOR.indd 65 10/12/2024 10:45:50

 READY TO
FUEL YOUR
KNOWLEDGE
ON SAF
Season 6 of the Fuel for Thought Podcast has kicked off
with 3 SAF Special episodes focusing on decarbonization
of the aviation industry. Scan the QR code and listen in or
find the episode in your podcast player.

SAF Special #1 of 3 From combustion to contrails:

Unveiling jet fuel mysteries
Get ready for a much-needed deep dive into the science and chemistry of
jet fuels to understand the impact.
Joined by Patrick LeClercq, Head of Department Multiphase Flows
and Alternative Fuels, at German Aerospace Center

SAF Special #2 of 3 Sky-high ambitions:

Investing in the future of Sustainable Aviation Fuel
What are the challenges and opportunities in financing SAF projects?
And what are the best strategies for reaching final investment decision?
Joined by Ladan Pazhouhandeh, Senior Investment Officer and
Kelly H. Johnson, Global Sector Lead in Chemicals and Fertilizers, at IFC

SAF Special #3 of 3 Fast-tracking SAF:

Your complete guide to co-processing
Allow us to introduce the fastest pathway to begin your sustainable aviation fuel (SAF)
production: co-processing and how to tackle the key questions you might be facing.
Joined by Ranoo Pathak, Senior Technical Service Engineer, and
Ignacio Fabian Costa, Licensing Manager from Topsoe

topsoe.indd 1 09/12/2024 14:43:34

 Potential of renewable fuels and SAF
A discussion of current technologies that can allow pivoting from renewable diesel
to SAF and even revert to the full production of fossil fuels, as markets dictate

Woody Shiflett
Blue Ridge Consulting

T
he last decade has seen sustained demand growth
(see Figure 1) in renewable fuels, building on more 40
than two decades of technology development and

Demand (billion litres per year)

35
commercialisation. Many efforts have been built upon
30
the foundations of mature refining technologies such as
hydrotreating and hydrocracking or more direct and simple 25
processes such as transesterification to produce fatty acid 20
methyl esters (FAME) for mainly biodiesel applications.
15
Production of sustainable aviation fuel (SAF) has certainly
lagged in absolute volume terms compared to renewable 10
diesel (RD) and biodiesel (BD). More recently, however, SAF 5
has shown notable growth rates, especially considering its
0
small production volumes a few years ago (see Figure 2). 2011-16 2017-22 2023-28
Currently, the RD and BD domains are facing challenges, Ethanol Biodiesel Renewable diesel Biojet fuel
notably the collapse of US renewable identification num-
bers (RIN) pricing (see Figure 3), an oversupply of BD/RD
in the EU, and announced plant closures or repurposing.3,5 Figure 1 Five-year growth in renewable fuels3

SAF potential contrasted with the corresponding IEA projection for ‘only’
Against this backdrop, could SAF serve as a refuge and 200% growth in RD to 26.4 billion litres/year (455,000 bar-
placeholder in the renewables arena, given its global infra- rels/day), or about 1.5% of projected demand.
structure and existing commercial and regulatory com- The International Air Transport Association (IATA) issued
mitments? This potential, regarding anticipated future an even more bullish recommendation to reduce aviation
demand, will be examined along with current technologies carbon intensity by 5% by 2030. This was agreed during
that can enable a pivot from RD to SAF, with the ability to the Third Conference on Aviation and Alternative Fuels
even revert to the full production of fossil fuels, as markets (CAAF/3 – November 2023), calling for 17.5 billion litres/
dictate. year (300,000 barrels/day) by 2030. Additionally, the US
There may be some basis for starry-eyed optimism for Departments of Energy, Transportation, and Agriculture
significant SAF growth within this decade. In its base case (DOE, DOT, and USDA) have formulated a SAF Grand
scenario, the International Energy Agency (IEA) projects a Challenge, aiming for domestic SAF production to reach 3
2,600% growth in global SAF demand from 2023 to 2028, billion gallons (11 billion litres/year or 200,000 barrels/day)
rising to approximately 5.2 billion litres/year (~90,000 bar- annually by 2030.
rels/day), or about 1.1% of total projected demand. This is Regional uncertainty and differences in regulations,

2.00
*Projected $2.50
1.80
Real dollars per gallon

1.60
$2.00
Billion litres/year

1.40
1.20
$1.50
1.00
0.80 $1.00
0.60
Biomass based diesel
0.40 $0.50 (D4) RINs
0.20 ethanol (D6) RINs
0.00 $0.00
2016 2017 2018 2019 2020 2021 2022 2023 2024* 2019 2020 2021 2022 2023 2024

Figure 2 Growth in sustainable aviation fuel1,2 Figure 3 Collapse of US D4 RIN values

www.digitalrefining.com PTQ Q1 2025 67

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 Technology readiness level of some biojet fuel technologies

Biojet technology Company Feedstocks Capacity L/year Status

HEFA/HRJ Neste (Espoo, Finland) Veg. oil, UCO, animal fat 2B Operational
ENI (Rome, Italy) Veg. oil 155 M Operational
Valero Energy Corp. and Darling Ingredients Inc. Veg. oil, UCO, animal fat 2.13 B Operational
(Norco, CA, USA)
World Energy (Boston, MA, USA), AltAir Fuels Non-edible oil, 150 B Operational
(Paramount, CA, USA) waste oil
Total (Courbevoie, France) UCO, Veg oil. 453 M Operational
UPM (Helsinki, Finland) Crude tall oil 120 M Operational
Renewable Energy Group (Ames, IA, USA) High and low free
fatty acid feedstocks 284 M Operational
FT Fulcrum Bioenergy (Pleasanton, CA, USA) MSW 1.8 B Planned
Red Rock Biofuels (Fort Collins, CO, USA) Wood 909.2 M Planned
ATJ Swedish Biofuel Technology (Stockholm, Sweden) Ethanol 10 M Operational
Biochemtex (Ortona, Italy) Lignocellulosic biomass <10 M Operational
LanzaJet (Skokie, IL, USA) Ethanol 180 B Operational

Table 1

incentives, and subsidies for RD, contrasted with the more favoured because it conserves renewable carbon atoms
global, fungible nature of jet fuel, offer the potential to drive in the fuel being produced rather than in CO and CO₂ as
SAF production. Nonetheless, near-term projections still byproducts. Specific heterogeneous catalyst systems allow
put RD demand a factor of four or five above that for SAF, selectivity to the favoured reaction sequence, as will be
highlighting certain alternatives that could offer fuels pro- noted later.
viders some risk mitigation. Several points are key from Figure 4, including consid-
One set of alternatives, considering the vast hydropro- erably more hydrogen is consumed for the HDO path-
cessing infrastructure in place for the production of fossil way than in fossil fuel hydrotreating operations (four to
fuels, is hydroprocessing paths. These are often denoted as five times greater), more even in the range beyond most
HEFA-SPK (hydrotreated esters and fatty acids to synthetic hydrocracking operations (up to twice as much). The pro-
paraffinic kerosene) or HRJ (hydroprocessed renewable duction of water by deoxygenating fatty acid chains and
jet). Hydrotreated vegetable oil (HVO) is another generic the saturation of olefin bonds are highly exothermic. This
term used to describe diesel and jet range products despite predicates a hydrogen supply not only for chemical con-
the implication that animal fats are excluded. sumption but also for quench gas, the latter depending on
Technically, HVO is a HEFA; hence, the latter term is more how much liquid recycle is employed to control tempera-
inclusive. Co-processing routes to SAF, as well as revamped ture rise.
hydrotreaters and hydrocrackers for full renewables pro- High amounts of propane, water, carbon monoxide,
duction, allow not only selectivity adjustment to yields for carbon dioxide, and methane off-gases are generated
SAF and RD but can also enable a total pivot between fossil compared to fossil fuel hydroprocessing. The various lipid
fuel production and renewable fuel production as market sources for HEFA contain a myriad of variable contami-
climate and regulatory pace dictate. nants that must be removed to tenable levels for hydropro-
High SAF yield technologies, approaching 100% or more cessing. Table 2 lists typical contaminants and levels and
liquid yield from renewable feedstocks, merit consideration the range of levels specified by technology providers for
such as ethanol-to-jet (ATJ-SPK) and gas-to-liquids (GTL- their hydroprocessing systems.8
SPK) production of SAF. Significant projects are underway Contaminant metals include alkali and alkali earth metals
for the latter two paths. Table 1 (adapted from reference 6) (Na, K, Ca, Mg) that are often part of acid salts, as well as
provides some perspective on players and technologies. It Fe, B, Si, Zn, and Al. The presence of phospholipids, com-
should be noted that some of the companies listed are no pounds similar to triglycerides except one fatty acid chain
longer financially stable. has been replaced by a phosphate group chain, in renew-
able feeds can be an issue in deactivation by phosphorus,
Fundamental chemistry of HEFA processes even at parts per million levels. Operators of HEFA units
The first step in SAF production is the complete hydro- must either install pretreatment units (PTUs) or purchase
genation and deoxygenation of the lipid triglycerides found pretreated renewable feedstocks.
in the renewable feeds that have been pretreated to make When considering the fatty acid chain composition range
them suitable for hydroprocessing. The triglycerides are of a number of representative renewable feedstocks, it is
comprised of three linear fatty acid chains bound by a glyc- easily noted that the resultant paraffin products from HEFA
erol backbone. Figure 47 illustrates the potential reaction processes will produce a significant amount of C18+ (and
pathways for a representative triglyceride molecule found C17 paraffins if appreciable decarboxylation occurs), which
in rapeseed oil. The hydrodeoxygenation path (HDO) is exceeds the desirable C8-C16 range for jet fuel. This dictates

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 HDO pathway products
~550 Nm3/m3
(3,300 SCFB)
Octadecane

Octadecane
HDO
+16H2
Docosane

O Rapeseed oil

O O 9c – Oleic acid CO2 + H2 H2O + CO Reverse water-gas shift

O O 13c – Erucic acid CO + 3H2 H2O + CH4 Methanation

O 9c12c – Linoleic acid

+7H2 Decarboxylation pathway products

Heptadecane
Decarboxylation

Heptadecane
~240 Nm3/m3
(1,440 SCFB)
Henicosane

Figure 4 Fundamental HEFA chemistry

that a hydrocracking component will be required in a HEFA- effect from the presence of phospholipids. The unit may
SPK process for SAF production. Furthermore, the product require some level of revamp to address the variability of
paraffin content is inadequate to meet the cold flow prop- feed acidity, higher product paraffin content, and the need
erties required for jet fuel needs. Hence, a hydroisomerisa- for adequate hydrogen and temperature control to handle
tion, or dewaxing, step will also be required. Fortunately, the higher oxygen and olefin content and concurrent reac-
existing hydroprocessing technologies can incorporate tion exotherms.
both, which will be discussed subsequently. The increase in off-gases will drive the need for higher
gas recycle rates and hydrogen addition rates to address
Co-processing renewables with fossil fuel feeds the higher purge rates needed to adequately keep CO lev-
For fossil fuel refiners, a straightforward entry into SAF els moderated and hydrogen-treat gas purity. CO is not
production is to utilise existing hydroprocessing units, removed by amine scrubbing, as is CO2, and it is a catalyst
appropriately modified, to co-process some percent- activity inhibitor. The combination of water and CO2 pro-
age of renewable feedstocks with petroleum feedstocks. duced can create carbonic acid downstream and needs to
Co-processing in hydrocracking and distillate hydrotreating be properly addressed.
units is an option that has been actively employed in refin- Concurrently, renewable feeds with high levels of free
ing scenarios for well over a decade.7 fatty acids pose corrosion issues in the feed systems analo-
Based on the chemistry, there are a variety of new chal- gous to high TAN fossil feeds. Several hydroprocessing unit
lenges compared to petroleum-based hydroprocessing types are amenable to some level of revamp to co-process,
units. These units must have specialised guard catalysts including kerosene hydrotreaters, diesel hydrotreaters,
and operating adjustments to assure the integrity of a cata- VGO (vacuum gas oil) hydrotreaters, and hydrocrackers.
lyst load cycle and mitigate effects from contaminants such The first three, likely with liquid recycle, will have some
as alkali and alkali earth metals (Na, K, Ca, Mg) and high flexibility toward SAF selectivity but will produce notable
acid content, as well as the strong phosphorus poisoning amounts of RD.9,10

Typical contaminants and levels and the range of levels specified by technology providers

Raw feed FFA, % P, ppm Metals, ppm CI, ppm Polyethylene, ppm
Vegetable oils <3 5-250 100-300 <5 –
Palm oill <6 15-30 20-60 <15 –
UCOs 1-10 <20 <50 20-100 0-200
Animal fats 2-35 50-1,000 200-2,000 50-500 0-1,000
Technology provider specs 5-20 2-3 5-10 5-50 50
FFA is free fatty acid content; metals include Ca, Mg, Fe, Na, K, B, Si, Zn, Al

Table 2

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 Hydrotreaters, in general, are not designed to be overly front-end layers of HDO catalyst can be Mo sulphides to
selective to any conversion to jet range material, owing mitigate exotherms and rapid hydrogen consumption as
to quench limitations and configuration. Single-stage, well as circumvent premature coking of the catalyst system
once-through hydrocrackers fall into a similar category. in addition to providing selectivity to the preferred HDO
Nonetheless, revamp activities can mitigate this problem. pathway, limiting CO and CO2 via decarboxylation.
However, the carbon chain length of the product must fall Sulphided NiMo/alumina catalysts have been used as
within the jet range, C8-C16, as excessive paraffins can lead higher activity components in the graded catalyst systems.
to not meeting jet freeze point specifications. Their preference is likely driven by a greater resistance
Even a kerosene hydrotreater will require modifications, to CO poisoning compared to sulphided CoMo/alumina.
the incorporation of dewaxing catalyst, and adequate Dewaxing in a single-stage system can be done using sul-
quench, at the very least, to be able to feed renewable feeds phided Ni, NiMo or NiW on a zeolite-containing support as
that produce paraffinic product within the jet boiling range is done with fossil fuel waxy diesel. In a two-stage system
that meet freeze point requirements. At least one technology where the second stage is sulphur-free, Pt or Pd on a zeo-
provider asserts that kerosene hydrotreater co-processing is lite-containing support is highly effective, as is the case for
the preferred cost-effective means to maximise SAF yield.7 fossil fuel diesel and jet.
Two-stage hydrocrackers have the most potential to both The question could be asked whether the sulphided base
maximise SAF yield concurrent with fossil fuel jet yield and metal HDO catalysts in current use are the optimum choice
retain the flexibility to adjust renewables content and selec- for the catalyst system in view of the added cost (and car-
tivity between diesel and jet. Technology providers have bon intensity) for sulphiding agent addition. Sulphided NiMo
given some guidelines on co-processing routes, as follows:10 and NiW catalysts are more active than their unsulphided
• Typically, <5% co-processing: counterparts. However, carbides, nitrides, and phosphides
 Requires feed rate adjustment or lower cycle length to have been studied and could yield potential. There are sig-
manage planned cycle. nificant driving forces for the continued use of sulphided
 No unit revamp; uses hydroprocessing catalyst system base metal catalysts:
with guard catalyst for renewable feed contaminants. • The activity of the sulphided catalysts is more than ade-
• Typically, 5-10% co-processing: quate for the purpose and aligns with existing design con-
 Requires minor compressor modifications and metal- ditions used in hydroprocessing unit technologies.
lurgy upgrades in a few locations. • Sulphided catalysts are fungible with existing fuels refin-
 Uses a tailored catalyst system, including significant ery hydroprocessing units and are employed in co-process-
guard catalyst for implementation. ing applications.
• Typically, 10-20% co-processing: • Economic products are in ready supply owing to a mas-
 Requires new equipment with metallurgy upgrades. sive manufacturing and support structure in place for the
 Uses a tailored catalyst system and guard catalysts. current hydroprocessing catalysts.
Approximate operational impacts of co-processing have • The scale of renewables units and their current demand
also been provided: support the existing inertia and provide little incentive for
• Some 40-50 Nm3/m3 (18-24 scf/bbl) of hydrogen con- a ‘boutique’ catalyst business based on formulations that
sumption per percentage of renewable co-processed. have yet to be commercialised.
• Roughly 3°C (5°F) temperature rise per percentage of
renewable in feed. Conclusions
• Propane yield about 0.2 wt% fresh feed per 5% renewa- Back to the question posed at the outset, ‘Is SAF a poten-
ble feed. tial a refuge and placeholder in the renewables arena?’ At
this point, with certain caveats, the answer is only ‘maybe’.
HEFA applications There are several sets of dynamics in play:
The catalysts and catalyst systems used for hydroprocess- • The European Union sets firm requirements in its direc-
ing renewables have been adapted from those currently tives for SAF (RED III), while the US employs incentives such
used in the hydrotreating and hydroconversion of fossil fuel as IRA tax credits and grants for SAF technology and pro-
feeds. As a result, they are sulphides of Group 6 (formerly duction. While the former may remain staunch in setting SAF
VIB) and Group 9 (formerly VIIIB) elements, such as Mo, demand and efforts in the EU, the new US Administration
W; Ni, and Co, supported on high surface areas, typically could potentially hinder future loan opportunities and tax
alumina, silica-alumina, or alumina-titania, for guard cata- credits for SAF producers and refiners. However, projects
lyst and HDO catalyst uses. There are also zeolites, such that have already secured funding commitments will con-
as ZSM-5, beta, and USY, for dewaxing and hydrocracking tinue as planned. Until recently, the US was previously pro-
function. Plus, all base metal systems need the addition of jected to produce 40% of global SAF supply through 2028.
sulphiding agents, such as DMDS, for processing pure or • Global airlines are making far-reaching and highly ambi-
near-pure renewable feeds with minimal sulphur content. tious commitments to SAF usage targets. These targets
For designs that comprise two stages (two separate gas are only single-digit percentages in near-term demand, but
recycling components), the second-stage catalyst typically growth in offtake agreements (21.7 billion litres in 2022
will be a noble metal (Pt or Pd) on a zeolite-containing agreements; 11.8 billion litres in 2023) puts substance to
support. Multi-catalyst graded systems are employed, and the commitments. Early producers with suitable economics

70 PTQ Q1 2025 www.digitalrefining.com

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 will enjoy the benefit. While SAF costs are multiples of cur- 2 IRENA emissions, as Reaching
(2021), shown inZero Table 2, resulted
with Renewables: in a Biojet
net saving
fuels, of
rent jet fuel prices,
3,000,000.00 € their low percentage usage will have
circa €2.7
International million
Renewable a year
Energy (the calculation
Agency, Abu includes
Dhabi. the cost of
Cumulative extra fuel gas (€)
minimal impact on the costNFIT of air travel. However, as SAF 3 Baker
Brelsford Hughes
R, Oil &Lifespan
Gas service
JouRDal, Mayand 24,antifoulant
2024. treatment).
www.ogj.com/
2,500,000.00 €
volumes grow, the willingness of air travellers to accept air- refining-processing/refining/operations/article/55039051/vertex-piv-
1.82˚C/month
LIFESPAN™, ASIT™ Asphaltene Stability Index Test, LSCI™ Lifespan
fare increases could be tested. At what point do traveller oting-mobile-refinery-hydrocracker-back-to-conventional-from-re-
2,000,000.00 € 0.40˚C/month
Concern Index, and LIFESPAN™ blending model are marks of Baker Hughes.
newable-service
costs override willingness
1,500,000.00 € to pay for SAF?
4 Bousso R, Reuters, July 2, 2024. www.reuters.com/business/
• The role of Chinese production could introduce another
1,000,000.00 € energy/shell-pause-construction-dutch-biofuels-facility-2024-07-02/
Giuseppe Della Sala is a Senior Technical Advisor for the Downstream
variable further down the road. European oversupply of BD, 5 Bloomberg. July 7, 2024. www.bloomberg.com/opinion/arti-
500,000.00 € Chemicals division of Baker Hughes, specialising in fouling for more
for example, was largely a consequence of 90% of China’s cles/2024-07-08/green-energy-the-biofuels-industry-bubble-is-de-
than 15 years. He is responsible for identifying on a case-by-case sce-
BD exports being - € sold into Europe at alleged dumping flating?embedded-checkout=true
0 50 100 150 200 250 300 350 400 nario, the best strategy required to eliminate or mitigate fouling in the
prices, likely resulting in EU tariffs of up to 36.4%. The 6 Peters M A, Tondo Alves C, Azubuike Onwudili J. 2023. A Review of
Days of run downstream industry, conducting data analysis and oil samples char-
potential for this in SAF is possible in the future, but current Current and Emerging Production Technologies for Biomass-Derived
acterisation, as well as supporting the development of future solution/
information suggests that Chinese SAF production will be Sustainable Aviation Fuels, Energies 16, no. 16: 6100. https://doi.
technology. He holds an MS in chemical engineering from Politecnico
onlyFigure
about6 1Cumulative
million mt extra fuel (1.3
per year gas due to preheat
billion fouling
litres/year) by org/10.3390/en16166100
di Milano University.
the end of 2025, some 2.5% of Chinese annual jet demand. 7 Perez M J L, Nygaard G T, Verdier S, SAF production via co-process-
Marco Respini is Senior Principal Chemist for the Downstream
day with
• Some biojetWTI processing
technologies andlower
offer without
risk the
entryBaker exit) ing in the kerosene hydrotreater, PTQ Q2 2024. https://ptqmagazines.
(and Hughes
Chemicals division of Baker Hughes with more than 25 years of expe-
digitalrefining.com/view/747650962/51/
antifoulant than
opportunities wasothers.
estimated (1.82°C/month)
As described – a figure that
earlier, co-process-
8 rienceV,inDe
Gibon crude
Greytoil
W,chemistry, processM,modelling,
De Kock J, Kellens Requirements and and
asphaltenes.
solutions He
ingwas extremely
in refining unitsreasonable
can be a from the RAM
low capital experience.
approach, albeitThe is the author of 20 journal and conference papers and an inventor of
for the pre-treatment of HVO feedstocks, Desmet. 2024. www.desmet.
decay
lower withtothe
volume, enterantifoulant program,and
the SAF business with
candosing rates
be easily 12 patents in the area of fouling control and renewables. He was pre-
com/images/DESMET_HVO_PRETREATMENT_BROCHURE_V2.pdf
terminated as markets dictate. Even complete revamps of of 9 Egeberg
optimised by the LSCI index, resulted in an NFIT decay viously aR,Research
Michaelsen Fellow at Milan
N, Skyum University
L, Zeuthen in the field ofinorgano-
P, Hydrotreating the
0.013°C/day
refinery units to(0.40°C/month)
produce renewables – a 78%can reduction
revert oftothe foul- production
fos- metallic ofcatalysis and is PTQ
green diesel, a member
Q2 2010.of the American Chemical Society.
sil ing
fuelimpact compared
production duringtopoor
the base case. economics, as 10 Ben
renewables Morgan
Honeywell UOP,is the Global 2023.
December Refining Leader for the Downstream
https://uop.honeywell.com/con-
Vertex Energy has done in Alabama with its hydrocracker.3 tent/dam/uop/en-us/documents/industry-solutions/renewable-fuels/
Chemicals division of Baker Hughes, specialising in refinery process
Economics
As a final observation, stakeholders with refining assets, Honeywell-UOP-Co-Processing-Technologies-web-brochure-final.pdf
chemical applications to enhance performance and equipment reliabil-
Baker
particularlyHughes
idled orand RAM calculated
underutilised the following
hydroprocessing, couldimpacts
very ity. He has more than 17 years of experience in the oil and gas industry
wellofinvestigate
fouling with theand without
‘maybe’ treatments
potential for SAFusing the previously Woody
production. and is currently
Shiflett involved
is the founderin crude
of Blueflexibility, technical support,
Ridge Consulting and trou-
LLC, specialis-
determined NFIT on fuel gas consumption and CO₂ emis- ing bleshooting in chemical engineering, inorganiccorrosion,
of refinery desalting, chemistryand andantifoulant
green chemistry,
issues. He
sions on a yearly basis, with a unit feed rate of 800 tons/h specifically
References holds a PhDdealing with hydroprocessing
in organic chemistry and catalysis
biocatalysisandfrom
process solu- of
University
(see Figure2023.
1 Renewables 6). IEA. International Energy Agency. www.iea.org/ tions. Shiflett holds a PhD in chemical engineering from the
Liverpool. He is currently a member of the Royal Society of ChemistryUniversity
The difference in fuel gas consumption and CO₂ of Wisconsin-Madison.
reports/renewables-2023/transport-biofuels and Chartered Chemist. Email: blueridgeconsulting2020@outlook.com
Email: ben.morgan@bakerhughes.com
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 FCC unit stripper design and
troubleshooting
Efficient removal of hydrocarbons from spent catalyst depends on multiple variables
and is influenced by stripper design, as shown in the following discussion
Warren Letzsch
FCC Consultant

T
he purpose of the fluid catalytic cracker (FCC) strip- Steam is added to displace the hydrocarbons in the strip-
per is to remove hydrocarbons from the spent cata- per. A pound-mole of steam has a volume of 379 SCF. If
lyst before it enters the regenerator or the catalyst the stripper is at 1,000ºF and 22 psig, the volume becomes
transfer line, which takes the spent catalyst to the regen- 425.5 ACF. Each pound of steam would have a volume of
erator. The catalyst leaves the reactor and flows as a mix- 23.6 ACF. These calculations can be made for any catalyst
ture of spent catalyst, hydrocarbons and dispersion steam. pore volume and density.
Steam is injected into the bottom of the stripper to push A stripper is really a series of mixing stages where the
the hydrocarbons that are in the interstitial space between catalyst and hydrocarbons flow down. A tracer such as
the catalyst particles back into the reactor, where they are helium injected into the top of the stripper can be measured
recovered in the FCC gas plant. Hydrocarbons can also be as the percentage going out the top and bottom (HO and Hi).
desorbed from the surface of the catalyst and some of the This is a measure of mixing efficiency but does not reflect
pores. The stripper also promotes further cracking reac- the desorption of the hydrocarbons from the catalyst.
tions, both thermal and catalytic. A model of the stripper was constructed and showed
The void space in the stripper can be determined from that adding all the steam to the bottom of the stripper gave
the density of the catalyst bed, the skeletal density of the better performance than splitting the steam with 50% to
catalyst, and the total pore volume (PV) of the catalyst. If a the bottom and 50% added at the middle. Perfect mixing is
cubic foot of catalyst in the stripper is considered, and the assumed for each stage. The overall efficiency (Eo) is:
weight of the gases is assumed to be negligible compared
to the weight of the catalyst, then: Eo = (1- (Heo/Hei)) (4)

Catalyst density = Volume of catalyst x Skeletal density (1) while each stage has an efficiency of:

Volume of the catalyst pores = Weight of the catalyst x Total Es = (1-Eo)1/n / 100 (5)
pore volume (2)
Stripper performance can be calculated from the stage
If the catalyst is not fluidised, then Equation 1 becomes: efficiency and the number of stages from Table 1. Eight

Catalyst apparent bulk density = Volume of catalyst x

Skeletal density (3) 3.40

3.20
The skeletal density is the density of the solid portion of
Skeletal density (gm/cc)

the catalyst (see Figure 1). Therefore, the density of the cata- 3.00
lyst divided by the skeletal density is the fraction of solids in a
2.80
cubic foot, and the rest is the total void space. From Equation
2, the total catalyst pore volume is calculated, and subtract- 2.60
ing from the total void volume gives the interstitial volume.
2.40
As an example, a catalyst with a density of 45 lb/ft3 and Most
catalysts
a skeletal density of 150 lb/ft3 has a total void of 70%. The 2.20
total pore volume is 0.30 gm/cm3, yielding 0.485 ft3 of pore
2.00
volume and 0.215 ft3 of interstitial volume. 0 20 40 60 80 100
For every 1,000 lb of catalyst circulated, the void space is: Wt. % Alumina

1,000 lb x 0.70 void space = 15.55 ACF Figure 1 Skeletal densities of silica-alumina cracking
45 lb/ft3 catalysts

www.digitalrefining.com PTQ Q1 2025 73

Letzsch.indd 73 10/12/2024 10:57:29

 100 1.00
8
4 Benzene
80 2
Percent displaced

0.80

Hydrocarbon stripped
1
60 Slurry
0.60
40
0.40
20
No. stages
0.20
0
0 1 2 3 4 5 6
Volume stripping/Volume emulsion gas 0.00
0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 100.0
Time (seconds)
Figure 2 Stripping at 500ºC

stages should give excellent performance and can be Figure 3 Expected performace from ideal stages
installed in most applications. A graphical representation
of this is shown in Figure 2. It suggests that ideally eight is high in hydrogen content and lowers the molecular
stages with a steam volume of two times the emulsion weight of the gas going to the wet gas compressor.
phase should be adequate. Higher reactor temperatures increase the desorption
In gasoil applications, the 2 lb/1,000 lb of catalyst cir- rate and reduce the time needed to effectively strip the
culated criteria works for disc and doughnut strippers catalyst. Reaction mix sampling can be used to assess the
operating within their design guidelines. These were 2-3 stripper performance and the amount of cracking occur-
lb steam/1000 lb catalyst circulated, a catalyst flux rate of ring downstream of the riser reactor. Cracking in the strip-
per will increase the delta coke and raise the regenerator
temperature.
Reaction mix sampling can be used The yield and operating changes used to calculate the
typical impact of a stripper revamp are shown in Table 2. A
to assess the stripper performance higher regenerator temperature lowers the catalyst/oil ratio
and the amount of cracking and conversion. Gasoline declines, but decant oil (DO) and
occurring downstream of the dry gas both increase. The slightly lower coke yield is due to
the higher heat content (hydrogen) of the coke.
riser reactor These changes are significant but not large enough
to change out a disc and doughnut stripper with a larger
diameter to lower the flux rate. Most strippers operating
600-900 lb catalyst/ (ft² minute), and a catalyst residence with more than 7 wt % hydrogen in coke are well above the
time of 60-90 seconds. design catalyst flux rates. The pinch points in the disc and
Stripping tests in the laboratory for benzene and slurry at doughnut design cause high localised catalyst velocities
500ºC (932ºF) are shown in Figure 3. Both streams are aro- that impede the rise of small bubbles. They either coalesce
matic and represent the hardest to desorb hydrocarbons. into larger bubbles or get swept down the stripper to the
Benzene would be essentially inert in the stripper, while the catalyst exit. Individual bubbles rise according to their size,
slurry would thermally crack at the long residence times of as shown in Table 3. Higher values are observed with clus-
the catalyst stripper. Having a residence time longer than ters of bubbles. Replacing the shell of the stripper is very
90 seconds might give a lower hydrogen in coke but would expensive and results in a project having a three- to four-
add to the wet gas compressor load. The dry gas produced year payback. These payback times seldom get funding.

Overall efficiency

Stage efficiency Number of stages

1 2 3 4 5 6 7 8 9 10
10 10 19 27.1 34.4 41.0 46.9 52.2 57.0 61.3 65.2
20 20 36 48.8 59.0 67.2 73.8 79.0 83.2 86.6 89.3
30 30 51 65.7 76.0 83.2 88.2 91.7 94.2 95.9 97.1
40 40 64 78.4 87.0 92.2 95.3 97.2 98.3 99.0 99.4
50 50 75 87.5 93.8 96.9 98.5 99.2 99.6 99.8 99.9
60 60 84 93.6 97.4 98.9 99.5 99.8 99.9 100 100
70 70 91 97.3 99.2 99.8 99.9 100 100 100 100

Table 1

74 PTQ Q1 2025 www.digitalrefining.com

Letzsch.indd 74 10/12/2024 10:57:29

 If the cracker is operating at a catalyst circulation limit, a
revamp should be considered. Stripper improvement
Packings have been found to improve the mixing of the
8% H in coke 6% H in coke
catalyst and steam and run with a constant catalyst velocity
ROT, ºF 980 980
based on the superficial velocity of the vessel. An open area
Regen bed, ºF 1357 1339
of about 96% allows this to happen. High flux rates are well
Feed preheat, ºF 550 558
below the rise velocity of a one-inch bubble, and the strip-
C/O 5.87 6.13
per will perform hydrodynamically. Residence times of the
Delta coke 0.84 0.83
catalyst will be shorter at the higher flux rates, so a higher
bed level with heavier feeds may be necessary. Other vari- Wt% Vol% Wt% Vol%
ables that can be manipulated are the reactor temperature, Dry gas (+H2S) 4.46 4.21
the pore volume, and the pore structure of the catalyst.
Total LPG 18.10 29.12 18.29 29.47
More dispersion steam might also be tried.
Gasoline, TBP
cutpoint 680ºF 51.19 61.51 51.76 62.14
Stripper problems
The operation of the stripper may become unsatisfactory LCO, TBP
and require some troubleshooting. The amount of steam cutpoint 430ºF 16.47 15.95 16.06 15.52
going to the stripper should be checked. If the regenera- DO 4.85 4.03 4.57 3.79
tor temperature has increased, it is possible the steam rate Coke 4.93 5.11
has diminished. This would allow hydrocarbons into the Conversion 78.68 80.02 79.37 80.69
regenerator, which would burn hotter than the coke. Some
refiners have tried to control the regenerator temperature Table 2
by adjusting the steam rate.
When the delta coke was too low for the desired regen- operating stages may be too low to get the needed overall
erator operation, an easy fix was to cut back the stripping efficiency. This is indicated by the data in Table 1.
steam. More than one refiner has tried this and gone too
far, with the result of a very high regenerator temperature Verifying damage
(>1,600ºF). The resulting ecat was a 40/40, a total surface If there is suspected damage to the internals of the stripper,
area of 40, and an activity of 40. Hydrotreating the feed tracer studies can be carried out to check both the catalyst
was a frequent cause of this situation. Adding a cat feed and steam flows. Distribution of these components across
fired heater may be the best solution to rectify the problem. the bed both horizontally and vertically throughout the
There are better solutions available to correct this prob- stripper bed will provide key information. Gamma scans can
lem. The burning of reaction products is expensive and is be used to find bed heights and standpipe hydrodynamics.
just too difficult to control. Raising the feed temperature The level in the stripper may be a factor when the unit is
will work, and the use of CO combustion promoters to let running. If the level is too low, the residence time may be
the CO burn in the regenerator bed rather the dilute phase insufficient to remove all the hydrocarbons. This could also
has been found to be effective. Increasing the bed depth result when a heavier feed is being processed or the unit
has helped to keep the CO conversion to CO₂ in the catalyst throughput is well above design. If the level is too high, the
bed. Higher catalyst activity or special high delta coke addi- catalyst flow may become erratic. If the cyclone diplegs are
tives will raise the bed temperature and are frequently used buried in the bed, the aeration around the diplegs may be
when bed temperatures need to be increased. impacted, such that catalyst separation is compromised. The
Problems with the steam distributor can cause maldistri- cyclones would have higher dipleg levels and could even
bution of the steam and spent catalyst. A power outage or flood. High catalyst losses to the main fractionator might
the loss of steam could lead to defluidisation of the stripper also be seen. Deeper fluid beds promote more channelling
bed and the plugging of some of the nozzles or the distrib- of the gas. Each stripper design has to be reviewed to locate
utor itself. When the steam and/or power is lost, the dis- potential operating limits.
tributor can fill with catalyst and may not clear itself when
the equipment is restored to working order. If the steam Bubble rise velocity
condenses, the wet catalyst may clump and plug orifices. It
helps to have drain holes in the distributor and some down- VB = 0.711 x gcDB
ward-directed nozzles to refluidise the stripper bed below
the distributor. All steam should be superheated, and water Bubble size Velocity
drains should be regularly used. (inches) (Ft/sec)
In extreme cases, the steam distributor breaks off, and all the 1 1.16
steam goes up one side of the stripper. With disc and dough- 2 1.65
nut designs, a fast turnaround is required to fix the unit. With 4 2.33
packing, the steam redistributes as it goes up the stripper. 6 2.85
By the time the fourth stage is encountered, the two phases
are mixed well again. The unit is operable, but the number of Table 3

www.digitalrefining.com PTQ Q1 2025 75

Letzsch.indd 75 10/12/2024 10:57:29

 A key operating parameter is the reactor pressure. Lower The lowest hydrogen content in the coke is 4 wt%,
pressures favour desorption of the oil molecules, as does though this number is unlikely. Numbers below 5.5 wt%
the hydrocarbon partial pressure. More dispersion steam are rare. The numbers above 7 wt% suggest that the oper-
can help start the stripping process in the riser reactor. As ation be examined, and possibly a revamp can be made to
feeds get heavier, the impact on the stripper becomes more consistently lower the number. Products are being burned
acute. Refiners are usually interested in processing more to hold the regenerator temperature up, and a revamp can
feed to improve profitability. easily be justified if the hydrogen value is 8 wt% or higher.
Over the years, capacity increases of 50% or more have If the catalyst flux rate exceeds 1,000 lb/(ft² minute),
been made. This generally is accomplished by raising increasing the steam rate can be tried, but it may not be
the reactor pressure to shrink the gases going to the gas effective. More variations of hydrogen content in coke
plant. When resid is part of the new feed, the stripper may seem to occur in FCC units adding oxygen to its air.
become the bottleneck. A catalyst cooler may be added to Accurate air rates are crucial since this figure, along with
control the regenerator temperature, but more oxygen will the oxygen content, is used to get the total oxygen going
be required for the additional coke burn. Higher catalyst cir- to the unit.
culation rates would call for a stripper design review. Flux rates through the stripper can also be too low. When
If the cat cracker makes 1 wt% coke more than necessary, units are oversized or running at 60-70% of capacity, the
the lost revenue would be about $800/day for every 1,000 steam rate might be reduced to match the cat circulation
barrels or $40,000/day for a 50,000 B/D FCC unit. This rate. Residence time in the stripper would be longer, which
assumes a barrel of products yield at $100 and fuel costs increases the thermal cracking. The quality of fluidisation
of $20 per barrel. In a year, this represents more than $14 would be poorer because of inferior mixing. The steam
million. The value of designing a new unit for lower pressure bubbles are the engine that stirs the catalyst bed. Low
should be considered when resid is going to be run. hydrogen on coke may reflect excessive thermal cracking
rather than better stripping. A higher steam rate as meas-
ured by (lb steam)/(1,000 lb of catalyst circulated) might be
If the cat cracker makes 1 wt% warranted.

coke more than necessary, the lost Stripper review

revenue would be about $800/day Another method of examining a stripper is to take samples
for every 1,000 barrels or $40,000/ from around it and test them for strippable hydrocarbons.
If a problem is detected, the operating parameters can be
day for a 50,000 B/D FCC unit checked for possible causes.
Periodic stripper checks can be made by lowering the
steam and watching for an increased regenerator temper-
Lower pressure makes more money by reducing the ature. The steam rate is increased by about 10% from the
coke produced and improving product distribution. Higher point where the temperature started to get higher. Any
octanes and olefins for alkylation are an additional bonus changes affecting coke make or delta coke warrant a strip-
due to reduced hydrogen transfer reactions. Better strip- per review.
ping and feed vaporisation are part of the equation. The
extra cost of the equipment due to larger vessel sizes is Literature cited
compensated for by the better yields. Between 14 and 20 1 Rall R, Kuralte R, Application of Koch-Glitsch KFBE Packing In FCCU
million dollars a year translates to 140-200 million dollars Catalyst strippers, Grace European Technology Conference, Seville,
in a decade of operation. Spain 2004.
The evaluation of a stripper’s performance is done in 2 Wilcox J, Optimizing Spent Catalyst Stripping to Enhance FCC unit
several ways. Lower hydrogen in coke is a typical indicator Performance, Albemarle, Issue 71, Courrier.
3 Baptista C, Cerqueira H S, Fusco J M, Chamberlain O R, What
of better operation. The flue gas analysis is critical to the
Happens in the FCC Stripper, NPRA, AM-04-53.
hydrogen analysis in coke because its value is determined
4 Schnaith M W, Improved Catalyst stripping From Cold Flow Modeling,
by oxygen disappearance. When an Orsat analysis was
Grace European Technology Conference, Dublin, Ireland 2002.
made of the flue gas, the CO and CO₂ solutions could be
5 Letzsch W S, Revitalize Stripping Operations with Structured
weak and not pick all of these molecules in the solutions.
Packings, Hydrocarbon Processing, Sept. 2003.
The unaccounted-for oxygen is assumed to be in the water
6 Private Communication, Lee Turpin.
formed in the regenerator.
7 Miller R, NPRA Transcript 2000, Heavy Oil Processing.
If the CO and CO₂ are low, the calculated coke make is low,
and the hydrogen-in-coke would be high. Good hydrogen- Warren S Letzsch has 56 years of experience in petroleum refining,
in-coke numbers range from 5.5 to 7.0 wt%. Later chroma- including petroleum catalysts, refining and engineering, and design.
tographs were found to give more consistent results than He has authored more than 100 technical papers and publications and
Orsats, and flue gas sampling devices improved. Refiners holds eight patents in the field of FCC. He holds BS and MS degrees in
control the excess oxygen in the flue gas to minimise after- chemical engineering from the Illinois Institute of Technology. Letzsch
burn and control SOx and NOx. Energy efficiency is also is a Fellow of the American Institute of Chemical Engineers.
improved. Email: wletzsch@verizon.net

76 PTQ Q1 2025 www.digitalrefining.com

Letzsch.indd 76 10/12/2024 10:57:29

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12:35 PM
 Improving energy performance of
instrument air system
Real-time case study wherein extended adsorption cycle times has led to reduced
fuel firing in a captive power plant and effective utilisation of energy
Subhosree Chakraborty and A Natarajan
Engineers India Limited

T
he underlying takeaway of the COP28 meeting, the Compressed air is one of the costliest utilities in any indus-
United Nations Climate Change Conference held in try. According to the Sankey diagram (see Figure 1), for
Dubai, UAE, in December 2023, stressed the need 100% electrical input energy, only around 15% is obtained
for greater energy efficiency and better energy utilisation as the useful output. This low return on electrically derived
processes. Such declarations are a positive development energy raises significant concerns, highlighting the need for
for the energy industry, especially considering that energy-​ energy optimisation in compressed air plant systems.
efficient solutions were historically not prioritised due to the One such area of energy conservation is utilising the heat
possibility of low return rates. The introduction of carbon of compression in air drying technology. The hot air from
costs (carbon incentives) can play a positive role in improv- the oil-free air compressor, at temperatures of 120°C or
ing overall economics. higher, can be used directly to regenerate the desiccant bed
This study will discuss an innovative approach to deter- in the compressed air dryer.
mining the cyclic switchover of the instrument air dryers The main advantage of a heat of compression (HOC)
in a refinery/petrochemical complex based on actual neces- type compressed air dryer is the energy conservation and
sity. For this purpose, a dew point analyser is specifically heat recovery that can be achieved. The energy that would
installed to monitor and regulate the sequence for dryer otherwise be wasted in a conventional air dryer’s after-
changeover. cooler is now used to reactivate the desiccant. HOC-type
As per case studies performed in-house, the implemen- air drying is an established practice that has been followed
tation of a dew point demand controller can lead to power in many fields over a considerable period. The focus now is
savings of 11-27% for an increase in tower changeover to identify opportunities for further improving the energy
time from one hour to three hours. This power saving efficiency of these existing facilities.
would reduce the overall power requirement of the com- The following approach will be discussed, wherein the
plex and subsequently result in less fuel gas being fired cyclic switchover of the air dryers will be determined on
in the complex’s captive power plant (CPP). A decrease in actual necessity rather than a predefined set point. For this
fuel gas consumption would subsequently reduce the CO₂ purpose, a dew point analyser is specifically installed to
emissions to the environment, in line with the decarbonisa- monitor and regulate the sequence for dryer changeover.
tion policy of the Government of India.
Compressed air system
Compressed air is generated at a centralised location in the
5%
plant and distributed to the various users through head-
Mechanical
losses ers. Two qualities of compressed air are produced and
80% distributed:
• Plant air is compressed air cooled to ambient tempera-
ture. Though it does not contain any entrained water drop-
Heat of
compression lets, it is saturated with water vapour at supply conditions.
Electrical
• Instrument air is used to operate various instruments in
energy 100%
(100 kW) the facility and to purge some control panels. Instrument air
15% is compressed air cooled to ambient temperature and dried
Useful output to remove water vapour to meet stringent atmospheric dew
point requirements (dew point at atmospheric pressure:
Air compressor
-40°C).
Moisture in instrument air can cause problems in the
operation of pneumatic systems, solenoid valves, and other
Figure 1 Sankey diagram depicts relatively low level of use- instruments and can adversely affect the process or prod-
ful output from electrical energy uct being manufactured. Thus, it is essential to dehumidify

78 PTQ Q1 2025 www.digitalrefining.com

EIL 1.indd 78 11/12/2024 11:39:54

 instrument air and meet its dew point specification before
usage. This is achieved with the help of an instrument air
dryer, which is explained in the subsequent section. Compressed air dryers

Instrument air dryer Refrigerant Desiccant Membrane

An instrument air dryer is a piece of equipment or machin-
ery used to dehumidify compressed (process) air to signif- Regenerative Deliquescent
icantly lessen or eliminate moisture in the air stream. The
most common types of dryers being used are based on the Pressure swing Heat of
adsorption principle, where the drying agent is a spheri- (Heatless/heated) compression

cal or granular form of material known as a ‘desiccant’ (see

Figure 2). The most common drying agents are silica gel,
molecular sieve, and activated alumina. Figure 2 Typical instrument air dryer system and related
The dryer selection is based on the mode of regeneration. functions
Generally, the air dryer utilises two towers: one containing
a desiccant that removes moisture from the air stream from advantage of a reduced water load since it continues to
the compressor, while the other regenerates the used des- regenerate at a predefined cycle time.
iccant. The main distinction between types of instrument
air dryers is based on the regeneration process, specifically Regulating dew point – an innovative approach
the ‘heat-reactivated regeneration system’ and the ‘heat- The dew point demand controller makes it possible to
less regeneration system.’ reduce the operating cost of any dryer by regulating the
In the heat regeneration system, the adsorbent is reused dew point rather than regulating the sequence through a
after desorbing its water vapour through either of the fixed time-based control panel. The outlet air dew point
means, such as: will determine the operating cycle time of the dryer. If the
• Direct heating of the adsorbent bed by passing hot air, dew point is higher than the desired level, the adsorp-
which is heated by an electrical heater. tion cycle can be extended beyond eight hours until the
• Indirect heating of adsorbent bed by embedded steam required dew point of -40°C is achieved. The controllers
coils in the adsorber through which steam is passed. can be set for the specific dew point desired in the system.
• Heating of adsorbent bed through the hot compressed air Changeover would take place only at the adjusted dew
(before air compressor aftercooler), utilising HOC. point.
The dew point demand controller utilises a state-of-the-
Instrument air dryer prevalent practice art moisture analyser to accurately measure the actual dew
Energy conservation by an HOC-type compressed air dryer point that the dryer is always delivering. The instrument
is a breakthrough in compressed air drying technology. The can also be set for a precise dew point at which the dryer
hot air from the oil-free air compressor at 120°C or higher is desired to switch towers. Every time a fixed cycle dryer
is used directly to regenerate the desiccant bed in the com- switches towers, it slightly damages the desiccant, thereby
pressed air dryer (see Figure 3). reducing its life. In addition, all the switching valves experi-
After regeneration, this air is cooled to 40°C in the water- ence wear and tear with every tower shift. Converting from
cooled aftercooler and then dried in the second tower. a fixed cycle to a demand cycle would increase the effective
Thus, the use of electrical heaters is avoided. The main life of desiccant and reduce the maintenance required on
advantages of HOC-type compressed air drying are energy the dryer’s switching valves. Overall benefits include:
conservation and heat recovery, which were wasted in the • Saving electrical power. Potential electrical power saving
aftercooler. Conventional ‘no purge loss type’ air dryers are in the dryer may vary from one to two years.
now being used to reactivate the desiccant. • There is no requirement for additional hardware to be
installed. Also, an analyser transmitter and soft signal to
Fixed-cycle dryer dryer PLC can predicate new requirements.
The instrument air dryers are designed for a fixed cycle • Because of the extended adsorption cycle time, the num-
time, where the switching from adsorption to regeneration ber of adsorption cycles/changeover will be reduced, and
mode takes place after a predefined set point to reach cycle the regeneration cycle also will be reduced. The extended
time. Dryers are mainly designed to function at maximum hours of operation of the adsorption cycle can also vary
operating conditions, the highest flow rate, the highest from ~10 minutes to three hours.
temperature, and the lowest pressure. • Reduction in the number of changeover cycles will, in
Fixed-cycle dryers are constantly switching towers and turn, reduce the wear and tear of the changeover valves,
regenerating based on worst-case scenario, whereas the control valves, and other components.
actual operating conditions may be quite different. With a • Operating efficiency of the air dryer will be high.
fixed-cycle dryer, regeneration is constant and designed
for the maximum incoming water load. In reality, the aver- Case study
age amount of moisture entering the dryer is less than The grassroots compressed air plant of a recently commis-
the design. However, the fixed-cycle dryer cannot take sioned Indian refinery is considered for the case study. The

www.digitalrefining.com PTQ Q1 2025 79

EIL 1.indd 79 11/12/2024 11:39:54

 Air compressor Air compressor outlet Regenerating
(After-cooler is bypassed) tower
Drying tower
Cooler assembly
HOC dryer intlet

Hot air
Adsorber-2
Adsorber-1 Exchanger Moist air
Moisture
separator

Dry air

HOC dryer outlet

Filter

Figure 3 HOC-type compressed air dryer schematic

baseline performance data of the instrument air dryer, which Conclusion

is designed for a fixed cycle time, is described as follows: India, the world’s third largest energy consumer, albeit
Baseline definition: instrument air dryer with fixed cycle with very low per capita figures, has shown tremendous
time zeal and commitment as part of international communities’
• No. of instrument air dryers: 4 @ 5,000 Nm3/hr efforts in combating climate change. Towards this end, the
• Heater rating per dryer: 160 KW honourable PM at COP26 presented Nationally Determined
• Adsorption cycle time: 8 hr Contribution (NDC) as five nectar elements (Panchamrit).
• Regeneration cycle time: 8 hr (6 hr heating + 2 hr The five elements briefly are:
cooling) u Reach 500 GW non-fossil energy capacity by 2030.
• Operating hours per annum: 8,760 hr v 50% of its energy requirements will be from renewable
• No. of adsorption cycles per year: 8,760/8 hr = 1,095 cycles energy by 2030.
w Reduction of total projected carbon emissions by one
One thousand ninety-five adsorption cycles in a dryer will billion tonnes from now to 2030.
require 1,095 regeneration cycles. x Reduction of the carbon intensity of the economy by
45% by 2030, over 2005 levels.
Post-retrofit with dew point feature: y Achieving the target of net zero emissions by 2070.
Dryer performance improvement Although transitioning to complete renewables or
By employing the ‘dew point demand controller’ in the dryer zero-carbon sources is the aim as technologies mature
system, the adsorption time is expected to be prolonged by and become cost-competitive, it is prudent in the interim to
one to three hours. The corresponding reduction in the regen- focus on opportunities towards improving the energy effi-
eration cycle and power savings are tabulated in Table 1 ciency of existing refinery facilities. Such improvements are
The data in the bespoke base case table validates the key to carbon emissions reduction as enshrined in the third
benefits of prolonging the adsorption cycle by one, two, and and fourth elements.
three hours. It infers that there is an appreciable amount of In the present opportunity, emphasis is being placed on
energy savings with the implementation of the dew point more effective energy usage in the hydrocarbon process-
feature in the instrument air dryer. Figure 4 illustrates energy ing industry. As a consequence, areas in which energy
savings (in %) achieved with an increase in cycle time. is wasted are being closely monitored, and methods for
By employing the ‘dew point demand controller’ in the energy recovery are being investigated.
dryer system, the average increment in adsorption time will Global average planet temperature has increased by
be in the order of 1.5 hours for at least the initial three years 1.5°C from pre-industrial times. India has made signifi-
of adsorbent life. cant efforts towards sustainable growth and outlined its

Post-retrofit with dew point feature: Dryer performance improvement

Parameter Base case Post-retrofit with dew point feature

(fixed cycle time) (adsorption cycle prolonged by)
1 hour 2 hours 3 hours
Regeneration cycle/annum 1,095 973 876 796
Reduction in regen cycle Base Base –122 Base – 219 Base – 299
Power for one dryer, MWhr/annum 1,051 934 841 764
Power savings per dryer, MWhr/annum Base Base – 117 Base –210 Base – 287

Table 1

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EIL 1.indd 80 11/12/2024 11:39:55

 Energy savings, %
27.2

20

11.1 Reactor & Tower

Internals, Custom
Fabrication
1 2 3
Cycle time increased by, hrs

Solutions at Your Service.

Figure 4 Adsorption time increases
wovenmetal.com
commitment towards net zero with the ‘Panchamrit’ goals. sales@wovenmetal.com
While India has committed to achieving net-zero emissions +1 281-331-4466
by 2070, its major players in the oil and gas sector have Alvin, Texas, USA
set their own goal of meeting net zero well ahead of the
national target. It is expected that emissions will increase
in the short term on account of business growth. However, Woven Metal Products (WMP)
scalable decarbonisation solutions are to be adopted at an provides solutions from inlet to outlet in all process
accelerated pace to align with the net-zero mission. conditions and vessel types. Our team understands the
Figure 4 illustrates that an implementation of a dew critical nature of reactors and towers and the value they
point demand controller can lead to a power saving of bring to your operations. That’s why we work to provide
11-27%, with an increase in tower changeover time from solutions as quickly as possible.
one hour to three hours. These power savings would
reduce the overall power requirement of the complex and Based in Alvin, Texas, USA, WMP has been a trusted
fabrication and manufacturing partner for companies of
subsequently result in less firing of fuel gas in the CPP.
all industries and sizes since 1967.
The decrease in fuel gas consumption in the firing of the
CPP would subsequently reduce CO₂ emissions to the
Call us today to discuss your reactor, tower and custom
environment, in line with the decarbonisation policy of the
fabrication needs: +1 281-331-4466.
Government of India.
Considering these advantages, the ‘dew point demand
control’ feature can be recommended for compliance in ‘no
purge loss type dryers’ and HOC-type dryers in the instru-
ment air dryer system.

This article is based on a paper titled ‘Compressed air dryer-guidelines

for selection and innovation’ published in Standards India Vol 5, March
1992 by Mr P. N. Misra.
WMP Solutions

Subhosree Chakraborty is Assistant General Manager in EIL’s Process Internals for Axial Flow Reactors:
department. She has more than 16 years of experience in refinery and Trays, Support Grids and Beams
petrochemical configuration, utility and off-site system design, energy
benchmarking, detailed and pre-feasibility studies, technology evalua- Internals for Radial Flow Reactors:
tion and licensor selection, and renewable energy. She has expertise in Scallops, Outer Baskets and Center Pipes
basic and detail engineering activities. Chakraborty holds a Bachelor’s
Separations & Filtration Products:
degree in chemical engineering from Kolkata.
Mist Eliminators, Liquid Coalescers and Bulk Mesh
Email: s.ghosh@eil.co.in
Mass Transfer Products:
A Natarajan is General Manager in EIL’s Static and Machinery Various Tower Tray Types, Packing and Support Devices
Equipment Department and handles packaged equipment/items. He
has more than 33 years of technical experience handling utility pack- Consignment Hardware Trailers and Lockers
ages/items for LNG plants, hydrocarbon refinery, and petrochemical
projects, detail engineering for utility items, and layout preparation for Custom Perforation / General Fabrication
utility packages. Natarajan holds a Bachelor’s degree in mechanical
engineering from Madaras University, Chennai.
Email: a.natarajan@eil.co.in Our Mission
Reliable Quality Partnership Attitude Attention to Detail

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 Corrosion mitigation of amine units
using MEA for deep CO2 removal: Part 1
Case study describing a gas plant experiencing high corrosion rates in the unit’s
major equipment, including the regenerator and contactor towers

David B Engel, Scott Williams and Cody Ridge

Nexo Solutions

A
mine units are under constant corrosion conditions
and must be closely monitored. A gas plant expe-
riencing high corrosion rates and increased corro-
sion rates used monoethanolamine (MEA) as a solvent to
remove H₂S and CO₂. Corrosion rates appeared to increase
over time as major equipment and probes were periodically
replaced. Corrosion was found in many areas of the unit,
including the regenerator and contactor towers. The lean/
rich heat exchanger and stainless steel probes also pre-
sented accelerated corrosion rates.
The inlet gas flow rate ranged from 10-13 MMSCFD (75 Figure 1 Thermal picture of the heat exchanger. White
psi), with only about 10-11 MMSCFD treated in the amine (>230ºF) orange-purple (<120ºF)
unit. The amine solvent flow rate varied from 45-55 GPM.
MEA often produces increased corrosion rates due to the Pictures of the amine unit were taken with a thermal
higher regeneration energy and the inherent increased cor- camera. While interesting findings were made, facility
rosivity of MEA and MEA salts in the solvent. The feed gas insulation hindered evaluation. Figure 1 shows the lean/rich
H₂S composition has decreased in the last couple of years, heat unit exchanger using a reference temperature range.
while the CO₂ concentration ranged from 1-1.5 mol%. The eight-tube pass heat exchanger had a two-shell pass
Table 1 shows the analytical history of the solvent. The for the lean solvent side of the exchanger. Normally, the
data indicated elevated chromium levels consistent with lean solvent should gradually decrease in temperature until
stainless steel corrosion and elevated iron levels consistent it exits the exchanger. However, it can be observed (Figure
with carbon steel corrosion. High acid gas loadings in the 1) that the lean amine solvent appears to flow downwards
solvent samples were contributing factors to the increased to the bottom of the exchanger prematurely, limiting heat
corrosion rates. The solvent loadings (lean and rich) were exchange area and efficiency.
higher than the maximum recommended values. For CO₂- This can explain why the rich solvent outlet temperature
only service, the maximum rich loading for MEA is 0.35 mol/ of the exchanger was found to be 160°F when the minimum
mol (without using corrosion inhibitors). Due to low H₂S temperature should be 195°F. This would suggest that the
concentrations, it is recommended that the rich loading be seal strips on the lean solvent side of the exchanger were
below 0.35 mol/mol. corroded, causing a bypass.

Amine solvent analysis

Sample Parameter Units 8/2020 7/2020 3/2020 2/2020 2/2020 12/2019 9/2019 12/2018
Lean amine pH -- 10.78 10.86 10.84 10.88 10.72 10.71 10.59 10.64
Lean amine Chromium mg/L 61.8 40 37.9 206 97.9 30.8 19.9 2.48
Lean amine Iron mg/L < 1.00 1.65 1.22 13.6 17.5 2.08 2.71 < 1.00
Lean amine Amine (GC) wt% 15.1 14.8 12.7 14 18.8 13.4 15.1 15.6
Lean amine Mol total acid mol% 0.1281 0.1265 0.1045 0.1002 0.121 0.0051 0.1307 0.1321
Gas/mol amine
Rich amine pH -- 10 9.98 9.56 9.81 9.89 9.82 9.49 9.81
Rich amine Mol total acid mol% 0.556 0.434 0.444 0.434 0.501 0.437 0.52 0.194
Gas/mol amine
Rich amine Mol H₂S/mol amine mol H₂S 0 0 0 0 0 0 0 0

Table 1

www.digitalrefining.com PTQ Q1 2025 83

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 Lone pair of electrons Lone pair of electrons

H N CH2 CH2 OH HO CH2 CH2 N CH2 CH2 OH

H H

Figure 2 MEA molecular structure Figure 3 DEA molecular structure

have also historically been used as corrosion inhibitors in

Lone pair of electrons
multiple processes. Nevertheless, when amines are sub-
jected to acid gas loading, the allowable strength must
HO CH2 CH2 N CH2 CH2 OH be limited based on how aggressively the amine and their
salts attack the metal surface. Laboratory data, in conjunc-
CH3 tion with plant data, indicate that as amine strength and
loadings are increased, corrosivity is enhanced. For this
Figure 4 MDEA molecular structure reason, MEA facilities should limit their amine strength to
a maximum of 20 wt%, their lean loading to a maximum
MEA is a primary amine and the strongest amine when of 0.15 mol/mol, and their rich loading to a maximum of
compared to secondary (diethanolamine, DEA) or tertiary 0.35 mol/mol. If there is H₂S present in the feed gas at a
(methyldiethanolamine, MDEA) amines. MEA has substi- concentration sufficient to form iron sulphide films in the
tuted one single ethanol group (CH₂-CH₂-OH), leaving two amine unit, then the rich loading could potentially reach
hydrogens attached to the nitrogen in the molecule (see 0.40 mol/mol.
Figure 2). All gas-treating amines (primary, secondary, or The plant has been operating below the maximum MEA
tertiary) react instantaneously with H₂S using their loan strength guideline of 20 wt%. In fact, the trend line for the
pair of electrons over the nitrogen. However, they all react strength has been dropping over the tested time frame.
differently towards CO₂. Regarding amine loading, both the lean and rich loadings
CO₂ replaces the hydrogen attached to the nitrogen in have been at the upper end of the recommended range, and
MEA. Thus, the presence of hydrogen in the MEA chemi- for the rich loading, in particular, the values have exceeded
cal structure means there are two active sites for the CO₂ recognised corrosion minimisation guidelines.
reaction. This makes MEA an attractive molecule for H2S As the trend line in Figure 6 shows, the rich loading (red)
removal and CO₂ removal in key applications. Typically, CO₂ has been trending upward. This is as expected since the
and H₂S can be removed to values less than 5 ppmV. The amine strength has been trending downwards. Since amine
loan pair electrons over the nitrogen in MEA are very active loading is described as moles of acid gas divided by moles
for reactions, especially with the steel and corrosion, thus of amine, a decline in amine strength will naturally result in
limiting solvent strength. an increase in loading. This is assuming the feed gas rates
In a secondary alkanolamine, such as DEA (see Figure and compositions are consistent over time.
3), the presence of the second ethanol molecule pulls the As the H₂S level in the feed gas has declined over time,
electron cloud away from the nitrogen, thus reducing its the ratio of CO₂ to H₂S in the rich solution has increased.
reactivity with steel. This is significant for several reasons, including the inability
In the tertiary amine MDEA (see Figure 4) compared to to lay down and maintain a protective iron sulphide passi-
DEA, the replacement of the third hydrogen with a methyl vation film and the inability to build a comparable iron car-
group hinders the acid-base reaction by steric hindrance, bonate protective film. Note that iron carbonate passivation
thus reducing reactivity and the overall intrinsic corrosion layers are less protective, more porous, and have a lower
tendency of the molecule. The result is the ability to operate mechanical strength.
MDEA at a strength of 50-55 wt%. Testing work presented During the site visit, the feed gas H2S content was 150
at a previous gas conference showed the relative corrosion ppmv and the CO₂ content was 1.0 mol%. The provided
tendencies of the three types of alkanolamines in relation amine solvent flow rate of 53 GPM and a feed gas rate of
to their concentrations (see Figure 5). Typical acceptable 11 MMSCFD resulted in a rich loading of 0.275 mol/mol CO₂
corrosion rates for amine units are <5 mils/yr. and 0.003 mol/mol H₂S for a total rich loading of 0.278 mol/
To get measurable corrosion rates in the study related to mol. This is a sizeable discrepancy between the reported
Figure 5, the testing was done at elevated temperatures in rich amine loading and the simulated rich amine loading.
a continuous CO₂ atmosphere. In a primarily CO₂ service Possible reasons for the discrepancy could be:
amine unit, such as at the gas plant from this case, CO₂ cor- u There is more CO₂ in the feed gas than determined (this
rosion can occur in any zone where the CO₂ partial pressure value was used in the simulation).
is high, temperatures are elevated, or solvent velocities are v The plant is processing close to twice the reported 11
high. Any combination of two to three of these factors will MMSCFD.
result in very severe corrosion events. w The plant is circulating close to half the reported 53
Amine solvents, in general, have low corrosivity. Amines GPM of MEA solvent.

84 PTQ Q1 2025 www.digitalrefining.com

NEXO.indd 84 11/12/2024 11:43:01

 35
0.6
30
MPY (microns/year)

0.5
25
20 0.4
15
0.3
10
5 0.2

0 0.1
EA

EA

A
DE

DE

DE

DE
M

M
%

%
%

0
50

20

%
30

15

50

30
Solvent type

20

20

/2 0
/1 20

/9 9
/1 19

/7 8
7/ 18

/5 8

/2 8

/1 8
8
02

02

19 01

18 201

25 01

1
30 01
01
20

20

26 /20

14 20

0
20

0
/2

/2

2
/2

/2

/2

/2
8/

7/

2/

/
2/

0/

6/
/3

/2
3/

1/

/1
16

25

11

11

16
Figure 5 Relative corrosion tendencies of alkanolamines Lean
loading
Rich
loading
Linear
(Lean loading)
Linear
(Rich loading)
(Depart, LRGCC 1991). Hot skin corrosion test, CO₂
atmosphere, carbon steel, seven-day test @210°F
Figure 6 Historic MEA lean and rich loading
x The MEA strength is lower than the reported value.
y The plant loading data is inaccurate. The lower the pressure, the lower the equilibrium loading
It is important to understand that the analysed rich limit. The gas plant amine unit will reach the maximum
amine loading is most likely lower than the actual oper- equilibrium loading faster than a high-pressure plant, so
ating loading. This is because a portion of the acid gas is high rich loadings are problematic for this facility.
always flashed off during sample capture, transportation, Corrosion in high loading amine units using MEA solvents
and when the sample bottle is opened for the laboratory is primarily focused where the contactor maximum temper
analysis. This makes the simulation discrepancy even more ature occurs (bulge), which should be in the middle section
pronounced. of the contactor given the low absorption rates at the bot
If the laboratory data is to be believed, the chances of tom of the column. Thus, the corrosion would be more pro-
corroding the contactor and the rich amine piping is high. nounced at this location in the column.
Amines cannot infinitely absorb acid gases. At the contac- Part 2 of the article will discuss the chemical and pro-
tor pressure, there is an equilibrium loading limit for acid cess implication of the corrosion events taking place at the
gas to be absorbed by the solvent. Once this loading limit amine unit in more detail.
is reached, no additional CO₂ or H₂S can be removed by the
MEA solvent regardless of how many trays are present in David Engel is the Managing Director of Nexo Solutions and has more
the contactor tower. Thus, there are two loading limits of than 25 years of industrial experience in a variety of areas of chemical
importance in regard to corrosion: engineering, material science and chemistry. He is the inventor of more
 The actual rich solvent loading. than 20 US Invention Patents and author of more than 100 techni-
v How close the rich solvent loading is to the equilibrium cal and scientific papers, and conferences. He has worked in several
maximum loading. technical and business capacities for companies such as Eastman
It is recommended to never exceed 80% of the equi- Kodak, Eli Lilly, and General Electric, and has recently specialised in
process optimisation and new technology development. He holds a BS
librium loading limit to avoid acid gas breaking out of the
in chemistry and a PhD in organic chemistry. He is Six Sigma certified
amine solvent in the contactor or in the rich piping, as the
and a member of several industrial committees and company board of
rich amine is heated or goes through pressure drops and
directors.
elbows in the piping. When the amine loading is too high,
any acid gas liberated from the rich solvent cannot be
Scott Williams is a process engineer and part of the Engineering
re-absorbed because it is already ‘too full’ at the conditions
Group at Nexo Solutions. He has been instrumental in many projects
present. This means the H₂S and CO₂ that were liberated
and solutions for the company and active in several R&D and engi-
are free to attack the steel surfaces in the unit, leading to neering initiatives. His latest focus is on liquid contaminant removal
corrosion. Since corrosion is a chemical reaction, increased from liquid and gas streams and selective separation applications. He
temperatures will increase the corrosion rates, meaning holds a BS in chemical and biological engineering from the University
rich amine corrosion and lean amine corrosion will primarily of Colorado at Boulder.
affect the hottest zones in the amine unit.
Pressure is important to an amine unit because it is vital Cody Ridge is a chemical engineer from Texas Tech and a lead pro-
for ‘pushing’ the CO₂ or H₂S from the gas phase into the cess engineer at Nexo Solutions. He started his career as an operator
liquid phase, where the reaction of H₂S and CO₂ with MEA and process engineer in the Permian Basin. He is responsible for field
occurs. The lower the operating pressure, the harder it is to engineering, technology development, and operations. He is the sup-
remove H₂S and CO₂ in the gas stream because the acid port engineer for the East Texas, Louisiana and Oklahoma region. He
gas partial pressure is very low (partial pressure is the sys- has more than five published papers and has consulted with 30+ gas
tem pressure factored by the mole fraction of CO₂ or H₂S). plants and refineries.

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 Technology in Action
Using CRA barriers to avoid metal Solution
IGS has partnered with this Qatar company since 2011
degradation in gas plants
and successfully prevented metal degradation in all its gas
When faced with metal wastage, asset owners and opera- processing equipment, including acid gas removal (AGR)
tors have viable options available to them in addressing amine absorber columns, AGR amine stripper columns,
the corrosion mechanisms with a corrosion resistance alloy fibre film contractors, flare knock-out (KO) drums, disul-
(CRA) barrier. The technique used to apply this CRA will phide oil (DSO) gravity separators, and mercaptan vessels.
mainly be determined by the shutdown time available to IGS provides a robust integrity solution in both very high
carry out the application. and low PH exposure conditions. This approach has proven
This case study explores a critical asset integrity chal- to be far superior to traditional thermal spray methods. While
lenge faced by a major Qatar gas plant, where severe metal some contractors might offer cheaper, conventional solu-
degradation threatened the operational efficiency and tions, the long-term performance demonstrates that such
safety of mission-critical gas processing equipment. short-term savings can lead to substantial future expenses.
During the January 2023 inspection, years after the initial
Problem HVTS application, protected vessels were found to be in
The Qatar gas plant produces and supplies natural gas and excellent condition. This mirrors findings from another gas
other hydrocarbon products from the Qatar North Field. plant where HVTS-treated columns remained undamaged
The company’s onshore plant is located on the Qatari coast after six years, while conventionally treated columns suf-
off the Arabian Gulf at Ras Laffan, about 80 km from the fered extreme corrosion and wall thickness loss.
capital, Doha. It has a total capacity of 2,600 MMSCFD of
reservoir fluid. The plant operates gas processing equip-
ment that was suffering from severe pitting of the carbon HVTS technology offers a
steel shell, exposed to process gas rich in H2S, and CO2.
Initially, there was some internal scepticism about the
sophisticated solution that
effectiveness of thermal spray technologies, citing previous addresses the complex corrosion
poor performance in similar industrial environments. This mechanisms inherent in demanding
scepticism is not uncommon in the industry, as highlighted
by other case studies demonstrating how conventional
industrial environments
low-velocity thermal spray can fail dramatically, resulting in
significant long-term costs compared to high-velocity ther-
mal spray (HVTS) technology. Conclusion
The decade-long partnership between IGS and the Qatar gas
Technological solution: Advanced HVTS plant demonstrates the transformative potential of advanced
Traditional thermal spray technologies often failed due to corrosion mitigation technologies. When confronted with
inherent limitations: permeability, internal stress, and weak critical asset integrity challenges, traditional repair meth-
bond strengths. IGS overcame these challenges when ods often fall short. HVTS technology offers a sophisticated
developing HVTS through: solution that addresses the complex corrosion mechanisms
• Supersonic particle atomisation (exceeding Mach 1). inherent in demanding industrial environments.
• Proprietary alloy composition modifications. Key takeaways include:
• Advanced chemical and process controls to prevent oxide • Proactive corrosion management can prevent millions in
formation. potential production losses.
• Precise surface preparation techniques. • Technological innovations like HVTS provide superior
The modified NiCrMoW alloy and HVTS process achieved protection compared to conventional methods.
corrosion performance comparable to premium wrought • Rigorous engineering standards and quality control are
alloy plates, with adhesion strengths ranging from 30 to crucial in developing reliable corrosion barrier solutions.
60 MPa. The success of this project underscores a critical insight:
investing in advanced asset integrity technologies is not an
Corrosion challenges expense but a strategic approach to maintaining operational
In industrial environments such as at the Qatar gas excellence, safety, and long-term economic performance.
plant, corrosion represents a significant economic threat. As these environments become increasingly challeng-
Maintenance-related issues can cause substantial produc- ing, innovative solutions like HVTS will play a pivotal role in
tion disruptions. In the oil and gas sector, corrosion mecha- extending equipment life, reducing maintenance costs, and
nisms are complex, involving factors such as acid-gas ensuring reliable operations.
ratios, contaminants, two-phase flow, and vessel design. Contact: rohit.kardile@integratedglobal.com

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