PTQ Q1 2025 Issue

REFINING GAS PROCESSING PETROCHEMICALS ptq Q1 2025

FCC UNIT STRIPPER TROUBLESHOOTING

ENERGY MANAGEMENT

HYDRODEOXYGENATION PATHWAYS

CORROSION MITIGATION

UPDATE YOUR SUBSCRIPTION REGISTER FOR A PRINT OR DIGITAL ISSUE TO MAKE SURE YOU CONTINUE RECEIVING A REGULAR ISSUE OF PTQ ANY QUESTIONS? REGISTER CONTACT US CLICK HERE

More than Waste

Discover Axens Solutions for Plastic Recycling

Q1 (Jan, Feb, Mar) 2025 www.digitalrefining.com ptq PETROLEUM TECHNOLOGY QUARTERLY

3 Downstream growth beyond 2025 Rene Gonzalez

5 ptq&a

19 Process control and energy management in the 21st century Jochen Geiger Ametek Process Instruments 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 – without the prior permission of the copyright owner. The opinions and views expressed by the authors in this publication are not necessarily those of the editor or publisher and while every care has been taken in the preparation of all material included in Petroleum Technology Quarterly and its supplements the publisher cannot be held responsible for any statements, opinions or views or for any inaccuracies.

www.decarbonisationtechnology.com www.digitalrefining.com

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. Learn more at catalysts.shell.com/MEMM.

Vol 30 No 1 Q1 (Jan, Feb, Mar) 2025 ptq PETROLEUM TECHNOLOGY QUARTERLY

Downstream growth beyond 2025

A 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 capital projects put on hold at the onset of the COVID pandemic, including at least seven LNG grassroots and expansion projects along the US Gulf Coast. Earlier last summer, Argus projected that three steam cracker projects in North 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 impacted by the combination of high-capacity increases and slower global economic growth. Regardless, the Middle East is experiencing a gas boom. Saudi Arabia plans to double its gas production capacity by 2030 and has awarded $25 billion in contracts to expand its natural gas production, aiming to increase gas sales by 60% to 2 bcf/day by 2030. Elsewhere, the completion of five refinery proj - ects in China through to 2028 is focused on the ability to pivot production from fuels to petrochemicals as market conditions warrant. Projects in Africa (such as the 650 kbpd Dangote refinery in Nigeria), India, and elsewhere will more than compensate for declining refining capacity in mature economies like Europe. Faced with a dwindling margin outlook, many refiners have simply opted to close their European refineries and refocus on other regions. The International Energy Agency (IEA) forecasts a closure risk of 1 to 1.5 million in Europe by 2030. However, the growing demand for sustainable aviation fuel (SAF) 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- ply. Besides competing with each other, the refining and petrochemical industry is competing for water resources with other industries such as steel, power, and data 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, exploitation of Argentina’s vast Vaca Muerta shale play is limited due to the lack of fresh water and pipeline infrastructure in that arid basin. Due to high levels of pollution in China’s seven major river systems, refiners there 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. This has led to a strong emphasis on water and energy conservation, with a focus on thermal systems (preheaters) and mass transfer units (pumparounds, reboilers). 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 demand in India will result in expanded FCC, hydrocracking, and hydrogen produc- tion to process a wide variety of imported crudes. The EIA estimates India’s liquid 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. However, mixed plastics pyoil upgrading first requires removal of chlorine, silicon, and other impurities. For example, upgraded hydrotreating systems are needed to remove total nitrogen, sulphur, oxygenates, and olefins saturation, but at reduced Capex/Opex, if possible. Incentives like the Waste Framework Directive and Global Plastics Treaty could accelerate these investments. Upgrading pyoil through steam cracking may be feasible, but further analysis of capabilities and financial modelling 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.

Editor Rene Gonzalez editor@petroleumtechnology.com tel: +1 713 449 5817

Managing Editor Rachel Storry rachel.storry@emap.com Editorial Assistant Lisa Harrison lisa.harrison@emap.com

Graphics Peter Harper

Business Development Director Paul Mason sales@petroleumtechnology.com tel: +44 7841 699431

Managing Director Richard Watts richard.watts@emap.com

Circulation Fran Havard circulation@petroleumtechnology. com

EMAP, 10th Floor, Southern House, Wellesley Grove, Croydon CR0 1XG tel +44 208 253 8695

PTQ (Petroleum Technology Quarterly) (ISSN No: 1632-363X, USPS No: 014-781) is published quarterly plus annual Catalysis edition by EMAP and is distributed in the US by SP/Asendia, 17B South Middlesex Avenue, Monroe NJ 08831. Periodicals postage paid at New Brunswick, NJ. Postmaster: send address changes to PTQ (Petroleum Technology Quarterly), 17B South Middlesex Avenue, Monroe NJ 08831. Back numbers available from the Publisher at $30 per copy inc postage.

Rene Gonzalez

PTQ Q1 2025

Rethinking Old Problems

More with Less

Revamp projects are difficult. Limitations imposed by plot space, congested pipe racks, and outdated equipment, to name a few, present unique challenges. Solutions that rely on excessive margins or comfortable designs lead to overspend. Now more than ever, process designers must find solutions that do more with less. P roven M ethods There is growing awareness that better scope definition earlier in the engineering phase saves time, reduces overall engineering cost, and leads to more successful projects. There is no argument that work completed during Conceptual and Feasibility phases is critical to getting a project on the right path. Engineers at Process Consulting Services, Inc. have developed a proven approach that makes the most of this precious time. At site, PCS engineers coordinate rigorous test runs, much 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 help you do more with less in your next revamp.

Projections for global supply and demand of refined products vary greatly depending on the pace of technological progress and degree of government policy enforcement associated with reducing greenhouse gas emissions. Without major advances in technology, it is hard to imagine a future without conventional fossil fuels over the next decade or two. Based on history, continued rationalization of refining assets is likely. Small, low-complexity refineries will struggle, while large, complex ones will thrive. Capacity creep through gradual improvement of refining units will continue to be a differentiating characteristic for remaining players. Focused revamps will play a critical role. Post-pandemic, inflation and a shortage of skilled construction labor have dramatically increased costs for refinery revamps. It is becoming increasingly difficult for many projects to meet corporate return on investment thresholds.

Field Measurements

3400 Bissonnet St. Suite 130 Houston, TX 77005, USA

+1 (713) 665-7046 info@revamps.com www.revamps.com

pt q&a

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

Q What are the optimal pathways towards increas- ing naphtha and LPG production (for petrochemical feedstocks)? A Mark Schmalfeld, Global Marketing Manager, mark. schmalfeld@basf.com, Hernando Salgado, Technical Service Manager IMEA, hernando.salgado@basf.com, and Alvin Chen, Global Technology Application Manager, alvin.u.chen@basf.com , BASF Refinery Catalysts Production of naphtha and liquefied petroleum gas (LPG) as petrochemical feedstocks is critical for meeting the demands of various industries. To increase the yield of these valuable products, a multifaceted approach is essen - tial, focusing on optimising processes, catalysts, and opera - tional parameters. Several optimal pathways can enhance the production of naphtha and LPG via fluid catalytic crack - ing (FCC), hydrocracking, and catalytic reforming. FCC is a widely utilised process for converting heavy hydrocarbons into lighter products. The selection of advanced zeolite-based catalysts is pivotal because they can significantly enhance selectivity towards naphtha and LPG. Innovations in catalyst composition, including the incorporation of specific metals or alterations to the pore structure, can lead to improved performance and greater product yields. Additionally, optimising reaction conditions such as temperature and pressure is crucial for maximising the production of lighter hydrocarbons. Higher temperatures generally favour LPG yield, while specific pressure adjustments can enhance naphtha pro - duction. High-severity FCC operation can further maximise light products (LPG, C2=) if the refinery has appropriate 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 design features, such as a dedicated riser to catalytically crack recycled naphtha to more light olefins or special riser terminations to increase residence time, are an additional handle to maximise light olefins production. Hydrocracking is another critical process that can be optimised to improve yields. The development of bifunc - tional catalysts that combine hydrogenation and crack - ing functionalities can enhance the conversion of heavier feedstocks into lighter products, such as naphtha and LPG. Furthermore, maintaining an adequate supply of hydrogen is essential for facilitating hydrocracking, which can further increase LPG yields from heavier fractions. Catalytic reforming processes also play a vital role in converting naphtha into high-octane gasoline components and generating aromatics. By adjusting catalyst properties and operating conditions, the catalytic reforming process can be optimised to maximise LPG yields as a byproduct while simultaneously improving the quality of gasoline components. Integrating reforming with other processes can recycle hydrogen and maximise the overall efficiency of

naphtha conversion, creating a more streamlined produc - tion chain. Utilising diverse feedstocks is also essential for enhancing naphtha and LPG yields. Employing a variety of feedstocks, including heavier crude fractions and biogenic sources, can lead to increased overall production. Tailoring processing conditions based on the characteristics of the feedstock can further optimise yields. Additionally, implementing pretreat - ment processes to remove impurities can enhance the qual - ity of the feedstock before it enters conversion units, thus improving the efficiency of subsequent processing steps. Effective heat and energy management strategies are a key consideration for lowering operational costs to make the economics of naphtha and LPG production more attrac - tive. Implementing heat integration and recovery systems minimises energy consumption during processing. Efficient energy use not only lowers operational costs but also enhances the economics of naphtha and LPG production. Optimising reactor designs for better thermal management can further improve conversion rates and increase product yields.

Effective heat and energy management strategies are a key consideration for lowering operational costs to make the economics of naphtha and LPG production more attractive

Leveraging data analytics can optimise production pro - cesses significantly. Utilising real-time data analytics and machine learning algorithms allows for continuous moni - toring and optimisation of production processes. Predictive maintenance and operational adjustments based on data insights can enhance overall efficiency. Additionally, devel - oping simulation models can help analyse various scenarios and optimise process parameters for maximum naphtha and LPG production. Incorporating sustainability into production processes is increasingly important. Exploring carbon capture and utili - sation technologies can minimise the environmental impact of increased production, thereby improving the sustain - ability of operations while maintaining high output levels. Investigating bio-based feedstocks and waste-to-energy technologies can also contribute to naphtha and LPG pro - duction, aligning with broader sustainability goals. In conclusion, to optimise the production of naphtha and LPG for petrochemical feedstocks, a comprehensive approach that encompasses advanced catalyst devel - opment, process optimisation, feedstock flexibility, and

PTQ Q1 2025

www.digitalrefining.com

innovative technologies is essential. By leveraging these pathways, the petrochemical industry can enhance the yield of these valuable products while improving both economic and environmental sustainability. The future of naphtha and LPG production lies in the integration of these strategies to meet the growing demand for petrochemical feedstocks in an environmentally responsible manner. A Carl Keeley, Head of Key Accounts, Global, Catalyst Technologies, carl.keeley@matthey.com, Marie Goret- Rana, Market Manager Additives, Catalyst Technologies, marie.goret-rana@matthey.com, and Jason Goodson, Regional Sales Manager Additives, Catalyst Technologies, jason.goodson@matthey.com, Johnson Matthey Naphtha is a fraction derived from crude oil and can also be obtained from natural gas condensates, petroleum dis- tillates, and other less common routes. It is primarily used to produce gasoline and as a feedstock for petrochemical products. LPG is commonly used for heating and cooking and includes products like propane, butane, and propane- butane blends. In addition to propane and butane, crude oil refining produces LPG olefins; these olefins are used to enhance gasoline quality and serve as feedstocks for pet- rochemical production. While gasoline demand is projected to decline as the US, Europe, and China adopt fuel alternatives and move towards a net zero economy, demand for naphtha and LPG for petrochemical production is expected to continue to grow ( source: bp Energy Outlook 2024 ). Crude oil is produced in many locations, with physical properties unique to the location from which it is extracted. Certain types of crude oil provide a higher yield of straight- run naphtha and LPG after distillation. By carefully selecting the crude oil blend to process, oil refineries can maximise naphtha and LPG production. In addition to crude oil distil- lation, oil refineries can use conversion process technolo - gies such as FCC to increase naphtha and LPG production. By optimising feedstock selection, equipment, process conditions, catalyst formulations, and additives, the FCC units can maximise naphtha and LPG yields depending on refinery economics. In general, FCC feeds are predomi - nantly paraffinic. Paraffinic feeds are easier to crack and normally provide the highest naphtha and LPG yields. Enhancements in feed injection, feed-catalyst mixing, and product and catalyst separation can boost naphtha yields. In addition, routing naphtha to a second reaction zone or dedicated riser can significantly increase LPG yields. Each FCC unit has its own operating window based on its available equipment and other constraints. Generally, high operating severity drives both thermal and catalytic cracking reactions. However, thermal cracking produces low-value byproducts like dry gas. Optimising FCC catalyst selection and incorporating additives enables the opera- tor to reduce operating severity and significantly increase naphtha and LPG production. Commercial FCC catalysts are engineered materials to optimise yields within unit constraints. The matrix materials perform the precracking of large molecules. The smaller, inter- mediate products produced can then enter the ultra-stable Y

(USY) zeolite, where they are further converted into naph- tha, LPG, dry gas, and coke. In addition to the FCC catalyst, specialist additives can be added to enhance LPG yield and increase propylene and butylenes production. Other addi- tives are available that enable operators to boost LPG olefins when FCC gasoline olefinicity is low. Utilising reliable and accurate catalyst and additive addi- tion systems is essential for optimising the addition of FCC catalyst and additives. Frequent, small additions are prefer- able to infrequent, large ones, as larger additions can upset FCC circulation and catalyst retention, leading to sub- optimal performance. Likewise, regular, small withdrawals of spent catalyst are recommended. Expertise in the cata- lyst and additive addition system design is crucial, as poorly designed systems can result in compromised safety and reliability, as well as reduced production of FCC naphtha and LPG. As refining markets continue to evolve, the operational flexibility of FCC units adapts accordingly, enabling refiners to remain competitive and profitable. The primary product streams consist of naphtha for gasoline production, along with naphtha and propylene for petrochemical production. Additional downstream naphtha and LPG olefins process - ing requires hydrogen and purification steps, requiring catalyst and absorbents. Q What type of flexibility can be built into a hydrocracker to quickly shift from naphtha to diesel output? A Heather Gilligan, Sr Hydroprocessing Engineer, heather.gilligan@imubit.com, Imubit Closed-loop artificial intelligence optimisation (AIO) technol - ogies, such as manipulated available handles (for example, reactor temperature and fractionator targets), drive towards a pre-computed optimal product mix based on a provided price set. This can occur for a single-unit or multi-unit sys- tem. The AIO model looks at economic objectives and con- straints, manipulating the handles to the optimal position to maximise the profit of the unit or the system as a whole. Moving from naphtha mode to diesel mode can have two transition points. The first is deconverting the tower to maxi - mise naphtha into the diesel cut, often to a flash constraint, once diesel is the more valued product. However, reduc- ing conversion/reactor temperatures to make more diesel frequently comes with a loss of liquid value gain, so diesel needs to have an even greater price advantage over naphtha before reducing reactor temperatures becomes attractive. Imubit’s AIO models are built on deep neural networks that ‘learn’ the nonlinear liquid volume gain and conversion curves associated with changing the reactor temperatures. This occurs not just at a single point in time but across the catalyst cycle as the catalyst deactivates, so the reactor stays optimised whether this transition occurs with fresh catalyst or just before the next changeout. A Peter Nymann, Senior Solution Specialist, Hydro- cracking, Clean Fuels, pan@topsoe, Topsoe In general, changes to the operation of a hydrocracker should never be made quickly due to safety concerns. It is

PTQ Q1 2025

www.digitalrefining.com

possible to operate a hydrocracker in ‘swing mode’ where the product objectives switch between maximising middle distillates (MDs) and maximising naphtha. This requires a margin in the operating temperature of the catalyst, so it should be a medium-to-high activity hydrocracking catalyst. If the unit is operated in recycle mode, maximum (‘max’) MD is favoured, and changing to once-through operation will lead to a switch to a higher naphtha produc- tion rate. High-activity catalyst may be installed in the latter part of the hydrocracking reactor, and the temperature profile may be changed from ‘equal-outlet’ to ‘ascending’ to move more conversion to the more active catalyst with a higher naph- tha selectivity. The change in temperature profile may be amplified in case the unit has several reactors, and a heat exchanger is installed between the two last reactors so that the high-activity hydrocracking catalyst can be oper- ated colder during max MD production and hotter during maximum naphtha production campaigns. It is important to check that the fractionation section, especially the overhead section and light ends recovery sections, can handle higher amounts of light material inad- vertently being produced during maximum naphtha pro- duction if the unit normally produces max MD. It should also be checked if the unit is able to provide the necessary lift of light material during max MD production in case normal operation is max naphtha. Hydrocrackers are, in general, very flexible, and a full range of catalysts from max MD to max naphtha production may be applied with the right expertise and safety considerations. A James Esteban, James.Esteban@unicatcatalyst.com, UNICAT Catalyst Technologies, LLC, Fu-Ming Lee, fmlee@ shinchuang.com, Tzong-Bin Lin, Maw-Tien Lee, Chi-Yao Chen, Mark Zih-Yao Shen, and Ricky Hsu, Shin Chuang Technology Co., Ltd In the ever-evolving landscape of hydroprocessing, the ability to adapt operations swiftly is paramount for refiners aiming to optimise production and meet market demands. A well-designed graded bed system, particularly utilising Unicat’s Advanced Filtration System (AFS) and MagAFS technologies, is essential for enhancing the operational flexibility of hydrocrackers. These systems not only opti - mise catalyst performance but also ensure that refiners can

respond effectively to changing product requirements, such as shifting from naphtha to diesel output. The design of the catalyst bed is fundamental to the efficiency and longevity of hydrocracking operations. AFS technology provides a unique solution by offering high available void space and optimised flow channels, mitigat - ing pressure drop, which is critical in maintaining consistent reactor performance. The AFS allows for uniform distribu- tion of reactants, ensuring that the catalyst operates at peak efficiency throughout its lifecycle. Refineries utilising AFS have reported significant improvements in operational metrics. For instance, one facility experienced a 150% increase in cycle length com- pared to traditional grading systems, leading to reduced downtime and enhanced profitability. This extended cycle life translates to lower operational costs and improved throughput, allowing refiners to maximise output without compromising product quality. Hydrocracker flexibility The flexibility built into hydrocracker operations through advanced catalyst systems like AFS and MagAFS is multi- faceted. The ability to quickly adjust operational parameters allows refiners to optimise yields based on real-time market conditions. When transitioning from naphtha to diesel pro- duction, the graded bed system can accommodate changes in feed composition and processing conditions without significant downtime. In one case, a refinery successfully shifted its output from naphtha to diesel within a matter of hours, thanks to the rapid response capabilities enabled by the AFS. This adaptability not only meets immediate mar- ket demands but also positions the refinery to capitalise on price fluctuations, enhancing overall profitability. Integration of demetalisation catalysts within the AFS framework enhances the ability to process a wider range of feedstocks. By effectively removing contaminants such as metals, these catalysts prolong the life of the primary hydrocracking catalysts and facilitate smoother transitions between different product outputs. Facilities employing Unicat’s demetalisation and grading catalysts have reported a minimum of a 30% reduction in catalyst replacement frequency, significantly lowering maintenance costs and improving operational efficiency. This reduction 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

26.86 wt% 9.49 wt% 843 ppm 0.43 wt% 0.53 wt% 224 ppm 1,529 ppm 1,337 ppm

12.67 wt% 14.78 wt%

98.9 96.2

100.0

Al Cr

2.16 wt% 2.14 wt%

87.6 90.0

100.0

Ni Cl

1.57 wt% 1.92 wt%

74.4 64.4

220 ppm

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

PTQ Q1 2025

www.digitalrefining.com

maintaining continuous production and meeting customer demands. Significant demetalisation of the feed to the hydro - cracker using MagAFS is seen in commercial operations on naphtha (light coal tar). This process has successfully demonstrated the removal of up to 98% total solids and 60-100% various metals in the feed steam, as shown in Table 1 . Although vanadium is not shown in the tested liquid stream, the mass susceptibility (magnetising characteristic) of V₂O₃ (1,976 x 10 -6 c.g.s. unit) is much higher than that of NiO (600 x 10 -6 c.g.s. unit). Therefore, V₂O₃ is easier than NiO to be removed by MagAFS. In conclusion, the implementation of a well-designed graded bed system using AFS and MagAFS technolo - gies is vital for enhancing the flexibility of hydrocracker operations. By ensuring optimal catalyst performance and facilitating quick adjustments in production outputs, these systems empower refiners to confidently navigate the com - plexities of the market effectively. The commercial perfor - mance results underscore the tangible benefits of these technologies, demonstrating that refiners can achieve lon - ger run lengths, lower pressure drops, and improved profit - ability. As industry continues to evolve, the importance of such innovative solutions will only grow, positioning refin - ers to meet both economic and environmental challenges head-on. Q How can the FCC unit be upgraded to benefit petro - chemical integration? A Delphine Le-Bars, Vice President Deep Conversion & Upgrading Product Line, Delphine.le-bars@axensgroup. com, Axens The FCC unit can be upgraded to benefit petrochemical integration through strategies ranging from some that can be easily applied to the existing FCC units to modifica - tions involving the implementation of new satellite units. An example of easy and quick implementation could be increasing severity and/or using specific catalyst formula - tions and additives (like ZSM-5 zeolite) with high selectivity to olefins. Other possibilities when evaluating unit modifi - cations to maximise olefins production include: • Incorporation of a separated riser (Petroriser) for light naphtha cracking recycling at a higher temperature (oper - ating under more severe conditions) than the main riser to maximise propylene production. • Integration of FlexEne technology, an innovative combi - nation of FCC and oligomerisation technologies, to expand the capabilities of the FCC process towards maximising olefins production. This flexibility is achieved by the oligo - merisation of light FCC alkenes (olefins) and recycling oligomerate for selective cracking in the FCC unit. The FlexEne concept can be easily implemented in existing FCC units. Investment in new FCC technologies, such as HS-FCC (high severity fluid catalytic cracking) technology, is an excellent prospect for olefins maximisation. The HS-FCC unit is an evolution of the well-known FCC process to reach

a considerably higher level of light olefins production, in particular propylene, to bridge the gap between refining and petrochemicals industries. Petroriser, FlexEne, and HS-FCC are marks of Axens. A Mark Schmalfeld, Global Marketing Manager, mark. schmalfeld@basf.com, Hernando Salgado, Technical Service Manager IMEA, hernando.salgado@basf.com, BASF Refinery Catalysts Upgrading the FCC unit can significantly enhance the inte - gration of petrochemical processes within refineries. The unit primarily converts heavy petroleum feedstocks into lighter, more valuable products like gasoline and diesel. However, by implementing specific upgrades, refineries can optimise the FCC unit to produce higher yields of pet - rochemical feedstocks, thus improving overall operational efficiency and profitability. Choosing advanced catalysts that are more selective towards lighter olefins, such as propylene and ethylene, can significantly increase the output of petrochemical pre - cursors. Some modern catalysts also have enhanced stabil - ity and longer lifetimes, reducing the frequency of catalyst replacement and downtime. Modifying the FCC unit’s riser section allows for better catalyst distribution and contact time with the feedstock. A design that promotes turbulent flow can enhance cata - lyst effectiveness by improving the distribution of catalyst within the unit. Special bed riser terminations can also increase residence time to increase reaction severity. The implementation of a secondary or dedicated riser to crack recycled light naphtha also can play a fundamental role in maximising light olefins yield, especially in the range of ethylene and propylene under severe reaction conditions. Additionally, upgrading to advanced catalyst injection systems ensures uniform dispersion and optimal contact between feed and catalyst. Upgrades to injection systems can also be beneficial when using new advanced catalysts. Adjusting operating conditions such as temperature, pressure, and feedstock composition can help in maxi - mising desired olefins production. Increasing the sever - ity of the cracking process can lead to higher yields of lighter products but requires careful balancing to avoid excessive coke formation and catalyst deactivation. High- temperature equipment such as reactors and advanced separators may need to be changed to handle the desired operational conditions. One particular feature that allows high light olefins yield is the reduction of the hydrocar - bons partial pressure by increasing steam streams to the reaction environment. This facilitates the equilibrium con - ditions to increase the conversion of heavy hydrocarbons to light olefin molecules. In this regard, some units maxi - mising light olefins operate within the range of 10-20% steam-to-feed ratio. Installing high-temperature reactors or modifying exist - ing reactors to handle elevated temperatures safely can improve the cracking of heavier feedstocks. Utilising high- efficiency separators can better recover lighter products, minimising the loss of valuable olefins.

PTQ Q1 2025

www.digitalrefining.com

Petrochemical integration Refineries can install downstream units such as olefin conversion units (OCUs), fractionators or propane dehy - drogenation (PDH) units that utilise the lighter products generated from the FCC. Another interesting integration is with steam cracking units (SCU) since ethylene produced by FCC can be recovered, while ethane can be further con - verted to ethylene in the SCU. Modifications to piping and the addition of heat exchangers may also be necessary to connect these units effectively to the existing FCC unit. This integration allows for a more seamless transition from refining to petrochemical production, effectively creating a more versatile and adaptable processing facility. Coprocessing biofeedstocks or lighter hydrocarbons alongside conventional feeds in the FCC unit can diversify the product slate. This method not only helps in meeting reg - ulatory requirements for renewable content but also allows for the production of unique petrochemical intermediates. Alternative feeds often require dedicated storage systems. Additional equipment modifications could include enhancing feedstock pretreatment systems to accommodate biofeed - stocks or lighter hydrocarbons. This might involve upgrading pumps and heat exchangers to handle different viscosities Coprocessing biofeedstocks or lighter hydrocarbons alongside conventional feeds in the FCC unit can diversify the product slate and properties of the new feedstocks. Additionally, FCC licensors have unique equipment modifications they can recommend for co-processing, particularly around how the alternative feedstocks are injected into the FCC. Implementing advanced process control systems can optimise the FCC unit’s performance in real-time. These systems can adjust parameters dynamically based on feed - stock variations and desired product specifications, maxi - mising yield and minimising waste. Many advance control systems are already available today in most refiners, such as real-time monitoring tools and automated control systems. This includes the installation of advanced sensors for tem - perature, pressure, and composition analysis to enable real- time adjustments and optimisation of the cracking process. Upgrades Advanced distributed control systems (DCS) upgrades can dynamically adjust operational parameters based on feed - stock characteristics and desired product yields, while upgrad - ing heat exchangers and integrating heat recovery systems can improve FCC unit energy efficiency. By capturing and reusing heat generated during the cracking process, refiner - ies can reduce overall energy consumption and enhance the economic viability of producing petrochemical products. Continuous investment in R&D can lead to the discov - ery of new catalysts, processes, and technologies that can further enhance FCC performance and its integration with

petrochemical production. Investments in new pilot plant equipment, testing equipment or modifications to existing designs are often needed to support new R&D innovations. By focusing on these upgrade strategies, refineries can - not only boost their FCC unit’s efficiency but also enhance their capability to produce a broader range of valuable pet - rochemical products, aligning with market demands and economic trends. A Carel Pouwels, Global FCC Specialist Light Olefins, carel.pouwels@ketjen.com, Ketjen For petrochemical integration, the maximisation of light olefins by the FCC unit is essential. Within a given unit con - figuration, the first choice is to enhance process conditions that maximise unit severity. Maximising reactor outlet tem - perature is one of the first independent process variables to consider; preferably, the temperature is enhanced to the range of 545-550°C. More extreme process conditions can be applied when the FCC unit is upgraded to so-called ‘high-severity’ FCC units, whereby reactor temperatures up to 600°C are possible. Depending on the metallurgy, a revamp might be needed. 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 refinery needs to expand with deC2, deC3, and deC4 recovery units while also building a C₃ splitter to make chemical-grade propylene. Next to the enhanced severity by a higher reactor tem - 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 - ecules are generated, which can be cracked to light olefins. Note, however, that hydrogen transfer reactions will also increase and can negatively impact C3=/LPG. The key to a high olefins yield is control of the various competing reac - tions. Hence, the reduction of hydrocarbon partial pressure through enhanced dispersion and lift steam is also of impor - tance. This way, light olefins are preserved, and reactions to paraffins by unwanted hydrogen transfer are minimised. While dedicated unit hardware and process conditions for high-severity operations are needed, the third element of importance is the FCC catalyst that is optimised for such application. While every FCC unit with its specific feed is unique, it thus requires a unique catalyst solution, prefer - ably from a repository of expertise with a wealth of industrial experience in high-severity FCC applications, ranging from the lightest to the heaviest feedstocks. With decades of sup - ply to various FCC units of all licensors, Ketjen’s max propyl - ene catalysts AFX and Denali AFX with optional usage of its DuraZOOM-MA additive, have achieved record olefins yields. Ketjen’s new ZSM-5 investment at its Bayport site will sup - port the industry in this move to petrochemical integration. A Fu-Ming Lee, Principal Author, fmlee@shinchuang. com, Shin Chuang Technology Co., Ltd, James Esteban, Sr Technical Manager, James.Esteban@unicatcatalyst. com, Unicat Catalyst Technologies, LLC To further upgrade the FCC unit for enhanced petrochemical

PTQ Q1 2025

www.digitalrefining.com

AHEAD A long history of looking

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

Original slurry oil (SO-O)

Treated slurry oil (SO-1)

nm(10 m) -9

nm(10 m) -9 *From similar particle size distribution (PSD) of SO-1 and SO-1A, it con r med only particle sizes smaller than 44.3 nm were left in the slurry oil after ltered by UMF lter.

Duplicate treated slurry oil (SO-1A)

nm(10 m) -9

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

integration, refiners can leverage a variety of advanced catalysts and technologies, including Magnetic Advanced Filtration System (MagAFS) and drop-in FCC catalyst addi- tive solutions. The following case summary focuses on a technology aimed at slurry oil (SO) upgrading. SO is one of the major FCC unit products, but with low quality and very limited applications, mainly due to its significant content of small catalyst fines (3,000-6,000 µg/g). Worldwide SO production from FCC units is huge in quan- tity. For example, even 25 years ago, FCC units in China

alone generated 5 million tons of SO annually. Therefore, the potential benefits of upgrading SO for petrochemical and fuel applications are substantial. Small catalyst fines, mostly smaller than 20 µm (10- 6m), in SO are extremely difficult to remove. Conventional methods, such as gravity sedimentation, centrifugal sepa- ration, filtration, and electrostatic precipitation, are inef- fective for fines removal, especially nanometer size (nm, 10-9m) particles. The development of an effective process for removing catalyst fines from SO to upgrade its qual- ity to transportation fuels and improved petrochemical applications is not only profitable but also environmentally preferred. MagAFS technology has been developed to remove par- ticles larger than 50 nm. The tests were conducted in a lab UMF unit consisting of two magnetic filtration chambers connected in series. Typical compositions of the tested SO are listed in Table 2 . SO was fed through the lab unit at a controlled flow rate. Treated SO samples at the exit of the first and sec- ond chambers were collected for particle size distribu- tion (PSD) analysis. Samples of solid particles removed by the first and second chambers were also collected for PSD analysis. Focusing on the nm size particles, PSD of the original SO (SO-O), treated SO (SO-1), and duplicate treated SO (SO-1A) are given in Figure 1 . It shows that with original SO (SO-O), more than 64% of the solid par- ticles were larger than 6,000 nm (or 6 µm). Only particles smaller than 44.3 nm were left in treated SO (SO-1). The result was confirmed by PSD in the duplicate treated SO (SO-1A). Further details of the operation are revealed in Figure

Typical compositions of the tested SO

Slurry oil source

Daqing 0.9690

Aramco 1.0162

Density, g/ml

Carbon residual, % Refractory index

4.95

7.27

1.5433

1.5797

Relative molecular weight

365

316

C, wt% H, wt% S, wt% N, wt%

87.92 10.72

88.11

9.41 1.66 0.48

0.33 <0.3

H/C

1.4528

1.2816

Ni, ppm V, ppm

1.8 0.1

8.4 2.6

Saturates, % Aromatics, %

53.3 41.9

26.7 67.0

Resin, %

4.1 0.7

4.9 1.4

Asphaltenes

Table 2

PTQ Q1 2025

www.digitalrefining.com

PSD of SO treated in 1st chamber

PSD of SO treated in 2nd chamber

nm(10 m) -9

PSD of solids removed in 1st chamber

PSD of solids removed in 2nd chamber

nm(10 m) -9

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

Q What FCC and hydrotreater modifications are needed to increase refinery coprocessing of renewable feedstocks? A Delphine Le-Bars, Vice President Deep Conversion and Upgrading Product Line, delphine.le-bars@axens- group.com, Marie-Amélie Lambert, Vice President, Hydroprocessing and Hydroconversion Product Line, marie.amelie.lambert@axensgroup.com, Benoît Durupt, Global Market Manager Hydroprocessing, benoit.durupt@ axensgroup.com, Dinesh-Kumar Khosla, Global Market Manager Hydrocracking and Resid Hydrotreatment, dinesh-kumar.khosla@axensgroup.com, Axens Renewable feeds available for co-processing in FCC units present different properties and impurities compared to conventional feedstock, impacting operation, heat bal - ance, catalyst activity, and unit performance. This impact will even depend on the co-processing ratio. The main

2 , where SO exiting the first chamber contained mainly 6-500 nm particles, but still had 20% 6,000+ nm par - ticles. SO exiting second chamber contained only 9-44 nm particles (no 6,000+ nm particles). Most larger par - ticles (2,600-6,000+ nm [63.3%]) were removed by the first chamber. Smaller particles (800-6,000+ nm [33.4%]) were removed by the second chamber. Figure 3 compares the PSD of the original (SO-O), treated (SO-1), and dupli - cate treated (SO-1A) slurry oil, based on the analysis of all samples collected from the experiments. The result confirmed that any solid particles having a size larger than 50 nm (44.3 nm) were successfully removed from the slurry oil by MagAFS process technol - ogy. It is also possible to provide low-cost and convenient on-site testing by installing a small portable MagAFS unit through a slip-stream connection without disruption to normal FCC unit operations.

Original

Treated

Duplicate treated SO-1A

SO-O

SO-1

nm(10 m) -9

Figure 3 Comparison of PSD of original and treated slurry oil

PTQ Q1 2025

www.digitalrefining.com

modifications that can be required in FCC units to increase the co-processing of renewable feedstock are dedicated feed injection nozzles, bio-oil storage and feed lines, and equipment materials upgrading. Dedicated feed injection nozzles, specifically for injecting fast pyrolysis bio-oil into the FCC riser, ensure refiners can co-process bio-oils while minimising potential plugging or corrosion due to mixtures of fossil and renewable feeds that might result in blending issues. The latter is due to the presence of many oxygen-containing molecules that result in a polar phase immiscible with fossil feedstock. Bio-oil storage and feed lines should be built with mate- rial resistant to corrosion over long-duration exposure to bio-oils feeds. For renewable feedstock, organic acid (RCOOH, which is measured by total acid number [TAN]) and chlorides are the main impurities that could cause cor- rosion issues. The long-chain organic acids usually pres- ent in these feedstock are weak acids that slightly acidify free water in contact with the feedstock, such as in storage systems. Equipment materials upgrading of the reaction sec- tion and main fractionation overhead section should be evaluated due to corrosion risks associated with chloride- containing compounds. Against this backdrop, the Axens technological solutions provide support in co-processing matters, offering feedstock characterisation, pilot plant tests, catalyst evaluation, and corrosion and revamp stud- ies to deal with the co-processing challenges related to the incorporation of renewable feedstock in commercial units. A Mark Schmalfeld, Global Marketing Manager, mark. schmalfeld@basf.com, Hernando Salgado, Technical Service Manager IMEA, hernando.salgado@basf.com, and Alvin Chen, Ph.D., Global Technology Application Manager, alvin.u.chen@basf.com , BASF Refinery Catalysts To increase the coprocessing of renewable feedstocks in FCC units and hydrotreaters, specific modifications are necessary to enhance compatibility, efficiency, and yield. Each modification must be tailored to the type of alter- native feedstock being processed, such as vegetable oils, animal fats, or other bio-based materials. The following discussion focuses on suggested modifications, their rel- evance to various feedstocks, and recommended pretreat- ment changes. FCC modifications Catalyst selection Modification: Use catalysts specifically designed for renew- able feedstocks, such as those that are more effective in cracking triglycerides found in vegetable oils. Relevance: Different feedstocks have varying molecular structures. For instance, vegetable oils require catalysts that promote the cracking of larger hydrocarbon chains into lighter fractions. Reactor design enhancements Modification: Implement dual riser reactors or modify exist- ing risers to allow for better mixing and residence time for alternative feeds.

Relevance: Lighter renewable feedstocks may require different flow dynamics compared to heavier petroleum feedstocks. Feed injection Modification: Install dedicated feed nozzles for renewable feedstocks. Relevance: Renewable feedstocks may not be stable at typical FCC feed conditions and may have to be handled differently (thermal stability, fouling, solution compatibility) to ensure reliable operation. Operating conditions adjustment Modification: Adjust temperature and pressure settings to optimise the processing of renewable feeds. Relevance: Each type of feedstock may have an optimal temperature and pressure range for effective cracking. For example, animal fats typically require slightly different con- ditions than vegetable oils. Relevance: Processing high concentrations of renewables (particularly bio-derived oils) can produce significant water, CO, and CO₂ yields in the riser. Hydrotreater modifications Hydrogen supply and management Downstream hardware modifications Modification: Increase sour water handling capacity. Modification: Upgrade hydrogen supply systems to ensure consistent and adequate hydrogen availability for the hydroprocessing of renewable feeds. Relevance: Many renewable feedstocks have higher oxy- gen content and thus require more hydrogen for effective hydrotreatment. Catalyst adaptation Modification: Utilise catalysts that are optimised for renew- able feedstocks, particularly those that can effectively remove oxygen and sulphur. Relevance: Different feeds, like palm oil vs used cooking oil, may require unique catalyst properties to achieve desired saturation and hydrodesulphurisation outcomes. Reactor configuration Modification: Modify existing reactors to accommodate higher flow rates and pressures, which can enhance the processing of lighter biofeedstocks. Relevance: Different feedstocks can have varying viscosi- ties; heavier oils might necessitate different reactor designs compared to lighter, more fluid alternatives. Pretreatment modifications De-oxygenation Modification: Implement de-oxygenation processes such as hydrotreatment or thermal treatment before feeding into the FCC, hydrotreater, or downstream equipment. Relevance: Reducing oxygen content can enhance yield and performance by minimising the formation of undesir- able byproducts during processing.

PTQ Q1 2025

www.digitalrefining.com

Page 1 Page 2 Page 3 Page 4 Page 5 Page 6 Page 7 Page 8 Page 9 Page 10 Page 11 Page 12 Page 13 Page 14 Page 15 Page 16 Page 17 Page 18 Page 19 Page 20 Page 21 Page 22 Page 23 Page 24 Page 25 Page 26 Page 27 Page 28 Page 29 Page 30 Page 31 Page 32 Page 33 Page 34 Page 35 Page 36 Page 37 Page 38 Page 39 Page 40 Page 41 Page 42 Page 43 Page 44 Page 45 Page 46 Page 47 Page 48 Page 49 Page 50 Page 51 Page 52 Page 53 Page 54 Page 55 Page 56 Page 57 Page 58 Page 59 Page 60 Page 61 Page 62 Page 63 Page 64 Page 65 Page 66 Page 67 Page 68 Page 69 Page 70 Page 71 Page 72 Page 73 Page 74 Page 75 Page 76 Page 77 Page 78 Page 79 Page 80 Page 81 Page 82 Page 83 Page 84 Page 85 Page 86 Page 87 Page 88 Page 89 Page 90 Page 91 Page 92 Page 93 Page 94