PTQ Q1 2024 Issue

REFINING GAS PROCESSING PETROCHEMICALS ptq Q1 2024

CONTROLLING BIOFILM FORMATION REFINERY WASTEWATER CHALLENGES

DIGITAL TWINS

CDU OPTIMISATION PREFLASH DRUMS & TOWERS

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Q1 (Jan, Feb, Mar) 2024 www.digitalrefining.com ptq PETROLEUM TECHNOLOGY QUARTERLY

3 Challenges to chemical recycling of plastic waste Rene Gonzalez 5 ptq&a 15 Adding CHP to refinery power infrastructures Rene Gonzalez PTQ 19 Filtration and separation for industrial carbon capture, transport, and storage Lara Heberle and Julien Plumail Pall Corporation 25 Overcoming wastewater challenges of opportunity crude processing Shane Lund Veolia Water Technologies & Solutions 31 Biofilm: A hidden threat Brian Martin Marathon Petroleum Corporation Tim Duncan and Gordon Johnson Solenis LLC 39 Simulating FCC upset operations Tek Sutikno Fluor Enterprises 45 Refractory detection system and floating roof protection Bob Poteet and Andrea Biava WIKA Haytham Al-Barrak and Mahendran Sella Saudi Aramco 51 Crude to chemicals: Part 2 Kandasamy M Sundaram, Ujjal K Mukherjee, Pedro M Santos and Ronald M Venner Lummus Technology 59 Revolutionising refining with digital twins Michelle Wicmandy, Jagadesh Donepudi and Rodolfo Tellez-Schmill KBC (A Yokogawa Company) 65 Optimising nitrogen utilisation in refinery operations Rajib Talukder and Prabhas K Mandal Aramco 75 Simulating VGO, WLO, and WCO co-hydroprocessing: Part 2 Mohamed S El-Sawy, Fatma H Ashour and Ahmed Refaat Cairo University Tarek M Aboul-Fotouh Al-Azhar University S A Hanafi Egyptian Petroleum Research Institute 81 Considerations for crude unit preflash drums and preflash towers

Henry Z Kister and Walter J Stupin (dec.) Fluor Maureen Price Maureen Price Consulting LLC 93 Technology in Action

Cover Large volumes of utility steam and cooling water are key to sustainable refinery and petrochemical operations, such as the unit shown on the front cover. Photo courtesy of Kurita Water Industries Ltd

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Ever-changing market conditions, global economic challenges, and the shared journey of the energy transition all mean it is crucial to evaluate easy-to-implement and cost- effective improvement opportunities. At Shell Catalysts & Technologies, our solutions open new possibilities for smarter investments while preserving cash through revamping, reconfiguring, or optimising your existing assets. Our experts co-create tailored solutions while keeping your margins in mind – ensuring the investments you make right now can help you maintain your competitive advantage into the future. Learn more at catalysts.shell.com/revamps. Revamp to thrive in the new reality

Vol 29 No 1 Q1 (Jan, Feb, Mar) 2024 ptq PETROLEUM TECHNOLOGY QUARTERLY

Challenges to chemical recycling of plastic waste

T he end products obtained through the chemical recycling of plastic wastes can be used as fuels, lubricants, or feedstocks for chemicals production, con- tributing to a more sustainable and circular economy. However, the efficiency and economic viability of chemical recycling processes can vary depending on the specific feedstock and the desired end products. The chemical recycling of pyrolysis oil (from plastic waste) typically involves refin - ing or upgrading the oil to improve its properties or convert it into specific chemicals. This can be done through processes such as hydrotreating, hydrocracking, and other chemical reactions. The goal is to produce higher-quality products that can be used as fuels, chemicals, or feedstocks for various industrial applications. However, some sceptics in Europe, the US, and elsewhere say the technical chal- lenges run much deeper than previously expected, including contaminants poison- ing of hydroprocessing catalysts, energy consumption, and emissions. The landscape of waste management and recycling initiatives can change rapidly, though, and new developments in one small pilot plant or research project could resolve these hurdles. Steady progress is expected in 2024 to fund scale-up to commercial production of chemical recycling of plastic waste-derived pyrolysis oil to its basic monomer. Although there are already proven technologies for producing propylene, polypro- pylene, and other plastics precursors, these are single-use, non-circular routes. Public campaigns to arrive at an international treaty limiting single-use plas- tics production coincide with calls for the implementation of Extended Producer Responsibility policies. This would make plastics manufacturers responsible for the entire life cycle of plastic products, and may incentivise resolutions of the many chal- lenges associated with expanding chemical recycling of plastic wastes. Despite the 2022 Inflation Reduction Act that could provide up to $1 trillion for ‘green’ investments (possibly including biomass or plastics chemical recycling to valuable products like PVC), billions of dollars continue to pour into the conventional fossil fuel industry, including refinery and petrochemical projects in the Middle East, Saudi Arabia, and China. Regardless of the increased use of EVs, solar, and other ‘green’ energy alternatives, global oil demand in 2024 is set to grow year on year by an impressive 2.2 million bpd, supported by steadily rising road mobility in major consuming countries, such as China, India, and the US. The IEA estimated growth in demand for petrochemical products means that petrochemicals are set to account for nearly half of growth in oil demand to 2050, ahead of diesel, SAF, and maritime fuel. It is no secret that refiners can sell fuels for $550/ton or else convert fossil-based feedstocks to petrochemicals and earn around $1,400/ton, such as with the integrated refinery and petrochemical facilities in India. Against this backdrop, it is projected that global production of thermoplastics will amount to 445.25 million metric tons per year (mmtpy) in 2025. Annual production volumes are expected to continue rising in the following decades to approximately 590 mmtpy by 2050. While the percentage from chemical recycling of plastic waste contributing to that 590 mmtpy seems insignificant, the fossil fuel industry seems confident that steady technical improvements will allow the upgrading of higher vol - umes of plastics waste-derived pyrolysis oil through refinery hydroprocessing units. The profitable link between plastics and fossil fuels may have provided a lifeline for Big Oil, including the refining industry. This begs the question: why invest in chemi - cal recycling of plastic waste? With the prospect of a global treaty that limits non- circular, single-use plastics production, it could be a big winner.

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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 Publisherat $30 per copy inc postage.

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PTQ Q1 2024

Vacuum tower cutpoint delivers profits

Cutpoint Concerns

poorly designed heaters may experience coking with COT below 700°F (370°C).

Crude unit vacuum tower performance is often critical to a refiner’s bottom line. e vacuum tower bottoms stream is valued far below the gas oil cuts, so most refineries look to minimize it. Many vacuum columns are also designed or revamped to produce a diesel cut, recovering diesel slipped from the atmospheric column that would otherwise be downgraded to VGO product. Good vacuum column performance can maximize the profitability of downstream units by removing distillate hydrotreater feed (diesel) from FCCU or hydrocracker feed (VGO) and removing VGO from coker feed (resid). One important measure of vacuum column performance is VGO/resid cutpoint. e cutpoint is the temperature on the crude TBP curve that corresponds to the vacuum tower resid yield. Vacuum column cutpoint depends on three variables: 1. Flash zone temperature 2. Flash zone pressure 3. Stripping section performance (if present) Flash zone temperature is driven by vacuum heater coil outlet temperature (COT). Increasing COT increases cutpoint. Vacuum heater outlet temperature is typically maximized against firing or coking limits. When processing relatively stable crudes, vacuum heaters with better designs and optimized coil steam can avoid coking even at very high COT (800°F+, 425°C), but

Flash zone pressure is set by vacuum system performance and column pressure drop. Lower flash zone pressure increases cutpoint until the tower shell C-factor limit is reached, at which point the packed beds begin to flood. Vacuum producing systems are mysterious to many in the industry, so a large number of refiners unnecessarily accept poor vacuum system performance. With technical understanding and a good field survey, the root causes of high tower operating pressure can be identified and remedied. In columns with stripping trays, stripping steam rate and tray performance are important. Stripping steam rate is limited by vacuum column diameter (C-factor) and vacuum system capacity. Any steam injected into the bottom of the tower will act as load to the vacuum system, so vacuum system size, tower operating pressure, and stripping steam rate must be optimized together. Depending on the design, a stripping section with 6 stripping trays can provide between zero and two theoretical stages of fractionation, which can drive a big improvement in VGO yield. Although the variables for maximizing vacuum tower cutpoint are simple, manipulating them to maximize cutpoint without sacrificing unit reliability is not. Contact Process Consulting Services, Inc. to learn how to maximize the performance of your vacuum unit.

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pt q&a

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

Q With the chemical value of hydrogen (H₂) increasing, what are the best options for extracting H₂ from fuel gas? A Neeraj Tiwari, Principal Process Engineer, Honeywell UOP, Neeraj.Tiwari@Honeywell.com High-yield byproducts generated by the refinery process for motor fuel, diesel or aromatics production can be high- value secondary revenue. The typical composition of fuel gas contains H 2 as ~30-50 mol%, and other major compo- nents are LPG range material. To monetise the benefit of these high-value byproducts and increase the overall prof- itability, a novel concept involving a dual sponge absorber can be applied to the off-gas stream (routed to fuel gas header) to recover the majority of LPG range material along with light naphtha, if any. The application of a novel dual sponge absorber will improve the hydrogen composition in off-gases to a high level (such as 70-85 mol%). This high-purity gas can then be routed to PSA to recover hydrogen efficiently having a purity of 99.9 mol%. In catalytic reforming, secondary byproducts generated include H₂, LPG, and fuel gas. Of these byproducts, the lowest value byproduct is generally fuel gas. UOP’s proprietary RecoveryMax system allows 95% recovery of hydrogen, >85% LPG recovery, and nearly 100% reformate recovery by purifying more of these byproducts and not diverting them to fuel gas. Alternative options are being explored based on where hydrogen is being used as one of the raw materials. One option is to contact the feed stream or any hydrocar - bon stream with hydrogen-rich fuel gas that will absorb the hydrogen; then, the absorbed hydrogen can be used during the reaction process. Concern with this option is that it can also absorb impuri- ties from fuel gas (such as C 1 , C 2 ), which may not be desir- able in the process. A Cristian Spica, Application Engineer, OLI Systems Hydrogen is an integral part of the modern energy industry and plays a crucial role in the path to net zero. Despite the strong momentum behind ‘green’ hydro - gen, to stay on track for achieving net zero emissions by 2050, we will need more than a doubling of the announced investments by 2030. These investments must mature and be put into action. Therefore, considering their significant economic advan - tages and as part of the short- to mid-term strategy to support the development of a clean hydrogen economy, we should make use of ‘grey’, ‘turquoise’, and especially ‘blue’ hydrogen production methods. Industrial technologies cur- rently employed for grey hydrogen production include: • Catalytic steam methane reforming (SMR) • Dry reforming (DR) • Catalytic partial oxidation (CPO)

• Autothermal reforming (ATR) • Tri-reforming (TR) • Coal/petroleum coke gasification/pyrolysis.

Blue hydrogen also relies on hydrocarbons but is com- bined with carbon capture, utilisation, and storage (CCUS) technology, which helps mitigate its environmental impact but may require additional investments. Turquoise hydrogen is produced through methane ther - mal pyrolysis. Each of these technologies has its own set of advantages and disadvantages based on the unique char - acteristics of the process. While SMR is one of the most established and widely used technologies for grey hydrogen production, it is also one of the most energy and capital-intensive processes. This is because the endothermic reaction in SMR requires heat, and the catalyst can suffer from deactivation if the fuel gas is not properly desulphurised. Additionally, in an SMR plant, there are two sources of CO₂ emissions: one from the oxidation of carbon atoms in the feedstock during reforming and shift reactions and the other from combustion in the reformer furnace. To capture all the CO₂, a post-combustion plant is required, as pre- combustion capture can only capture the CO₂ in the syngas. Despite these challenges, SMR is still considered one of the most efficient methods for producing grey hydrogen, especially when heat integration is part of the process design. The same efficiency advantage applies to DR, but it also faces the drawback of coke deposition on the catalyst surface. In the case of CPO, the partial oxidation of CH₄ and other hydrocarbons in the fuel gas is a slightly exo - thermic reaction, making it less capital-intensive than SMR. However, it initially produces less hydrogen and CO₂ per unit of input fuel compared to SMR. To produce high-purity H 2, pure oxygen or an air separation unit (ASU) is needed. ATR generates syngas by partially oxidising a hydrocar - bon feedstock with oxygen and steam, along with sub - sequent catalytic reforming. Unlike SMR, the heat for the reaction is provided within the reaction vessel, eliminating the need for an external furnace. This method allows up to 99% of carbon removal directly from the syngas, resulting in lower carbon capture costs. ATR, when combined with CO-shift and carbon capture technology, is one of the most cost-effective solutions for large-scale low-carbon hydro- gen production. TRM is a combination of SMR, CO₂ reforming, and PCO in a single reactor for efficient syngas production. The inclu - sion of oxygen in the reaction generates in-situ heat, which can enhance energy efficiency. However, it may present challenges in terms of heat transfer and temperature uni- formity in the catalyst bed. The choice of the best production process depends on several factors affecting both capital and operational expen - ditures, including hydrogen yield, purity, energy efficiency, flexibility, plant complexity, and raw material availability.

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ATR combines the advantages of both SMR and partial oxi- dation, offering a high hydrogen yield, rapid reaction kinet- ics, and reduced reactor number and size. OLI Systems provides unique tools for designing and safely operating grey and blue hydrogen facilities. These tools encompass a wide range of capabilities, including modelling for various production processes (SMR, ATR, TRM, CPO) for hydrogen storage, transportation, and CCUS. These tools offer rigorous mass balance, corrosion, and scaling risk assessment, considering the reactivity and phase equilibria of impurities and their potential negative impacts on plant safety and reliability. Hydrogen as well as CO₂ dense phase, especially when containing impurities, can promote corrosion in materials such as steel, pipelines, and storage tanks. Impurities like water vapour, oxygen, sulphur compounds, nitrogen compounds, and carbon monoxide can react with hydrogen to form corrosive sub- stances, making the selection of corrosion-resistant materi- als essential for hydrogen transportation infrastructure. Q What contaminants removal capabilities are available to expand the SAF feedstock base? A Yvon Bernard, Business Development Manager, Renewable Product Line, Yvon.BERNARD@axens. net, Yoeugourthen Hamlaoui, Global Market Manager, Yoeugourthen.HAMLAOUI@axens.net, Alexandre Javidi, Alcohol to Jet Business & Technology Manager, Alexandre. JAVIDI@axens.net, Axens u For SAF production from low-carbon ethanol through Axens’ proprietary Jetanol solution, one of the key Axens features (Atol) is an innovative and profitable technology due to its flexibility in handling a wide range of feedstocks. During the technology development, Axens, along with its partners IFPEN and TotalEnergies, developed customised analytical methods for mastering the ethanol impurities that are critical for this application. Extensive testing in pilot plants was also performed to confirm the technical ability to process virtually all kinds of ethanol: bioethanol (1G) or advanced ethanol (2G) and waste-based ethanol (from blast furnace flue gas and municipal solid waste) at various levels of dilution. Furthermore, Atol relies on its superior catalyst, which has proven to have a high tolerance to feedstock impurities and is fully regenerable. Atol catalyst provides even more flex - ibility by allowing the handling of feedstock quality fluctua - tions. In terms of ethanol, impurities are well-known and can be handled with pretreatment solutions. v For SAF production from lignocellulosic biomass via gas- ification route (BioTfueL), impurities are dealt with in three steps. The first is the pretreatment step, which ensures the removal of foreign contaminants such as glass, rocks, plas- tics, and moisture. Additionally, the pretreatment homoge- nises the biomass through drying and torrefaction: this step is key to enabling the utilisation of a wide array of lignocel- lulosic biomass, from agricultural residues to energy crops and forestry residues. In the second step, biomass gasifi - cation technology removes the inorganic (mineral, metals) and chlorine from the biomass.

The remaining S- or N-based impurities are removed in the syngas phase through well-known separation technologies. Its smart and flexible contaminant removal scheme allows BioTfueL to operate with any kind of biomass. This feature means more resilience for the project and gives significant flexibility in operation to the customers. Some additional feed - stock, like municipal solid wastes, brings other opportunities but requires additional pretreatment and purification steps to deal with the heterogeneity of the feedstock and impurities. w For SAF production from CO₂ and H₂, purity require - ments are often regulated by the downstream unit, mainly the Fischer-Tropsch reaction section for the e-fuel pro- duction. Axens dispatches its wide portfolio to cope with the common impurities found in CO₂ feedstock, including adsorbents for impurities trapping as well as washing sec- tions, to bring the feed to the desired specifications. The final scheme of purification will depend on CO₂ project qual - ity and is typically adapted on a case-by-case approach. Typical contaminants for FT catalyst are (sulphur, organic nitrogen, metal, NOx). Axens’ integrated scheme takes advantage of its expertise and know-how to optimise the sizing and positioning of such purification requirements. x For SAF production from vegetable oils with Vegan technology, pretreatment is also needed. Phospholipids and metals (Fe, Mg, K, Ca, Na) were the main contami- nants present in the first-generation vegetable oil (soybean oil, palm oil, rapeseed oil) and could be abated with well- established edible oil refining technologies. The processing of second-generation waste oil (used cooking oil, animal fats) brings a wide variety of contaminants, including the same contaminants as vegetable oil, but at higher content. Pretreatment technologies are adapting to remove con- taminants to acceptable levels. Higher nitrogen, sulphur and chlorine are also observed in these new feeds: nitro- gen/sulphur are partially removed by pretreatment and then converted by the hydrotreatment, inorganic chloride is com- pletely removed by pretreatment, whereas organic chloride slips to the hydroprocessing unit, which has an impact on the unit design and metallurgy selection. Polyethylene found mostly in animal fats should be removed in a dedi- cated section of the lipid feed pretreatment. A Andres Coy, Business Development Manager SAF, Syngas and Fuels, Andres.Coy@clariant.com, Rainer Albert Rakoczy, Technology Advisor Fuel and Hydrocarbons, Syngas and Fuels, Rainer.Rakoczy@clariant.com, Clariant Catalysts The potential feedstocks and process routes toward SAF are constantly increasing. Any SAF as a final Jet fuel blend - ing component must meet very stringent specifications, as aviation fuels are the most delicate fuel products in terms of quality and stability. In addition, most of these processes need optimum reactant properties to achieve the most effi - cient SAF yields. Clariant offers a broad variety of catalysts and adsorbents technology to clean most feed and inter- mediate species in gas or liquid phase for these SAF pro- cessing technologies. This technology is primarily based on long-time experience in handling non-benign and demand- ing feed streams even in industries beyond refinery.

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Turn iron into gold? Alchemy? No. It’s chemistry.

MIDAS ® Pro catalyst offers the solution for resid cracking in high iron environments. Gain feed

Grace, the global leader in FCC catalysts and additives, introduces MIDAS ® Pro catalyst, for resid cracking in high iron applications. This innovation, built on our workhorse MIDAS ® catalyst platform, proved its capacity to handle even the worst Fe excursions. In commercial trials with multiple in-unit applications, MIDAS ® Pro catalyst demonstrated sustained bottoms cracking in the face of iron spikes that measured among the highest in the industry. Diffusivity levels were consistently high, indicating no transport restrictions with concentration of Fe. This improved iron tolerance allows refiners to operate at higher iron levels which increases feed processing flexibility and profitability.

flexibility with better bottoms upgrading.

Talk with your Grace partner about the advantages of MIDAS ® Pro catalyst today. Learn more at grace.com

A Kandasamy Sundaram, Distinguished Technologist & Lummus Fellow, kandasamy.sundaram@lummustech.com SAF is addressed from different angles. Plastics pyrolysis, tyre pyrolysis, and vegetable oils are a few examples. They all have different types of contaminants compared with fossil fuels. Some adsorbents are used to remove some contami- nants. However, they are not able to reduce the concentration significantly. Hydrotreating is required. Isoterra for vegetable oil uses hydrotreating. Plastic pyoil requires hydrotreating to reduce chlorides and nitrogen. For chemicals production, adsorbents meet the specification in some cases. A Ezequiel Vicent, Senior Application Engineer and Consulting Lead, OLI Systems The advent of renewable fuels has brought the necessity to change catalyst to treat the carboxylic groups in the fatty acids that make up vegetable oils (increased CO, CO₂ and H₂O production) as well as an increase in chlorides. In addi - tion to catalyst selection, unit engineers need to focus on the production of the byproducts from these reactions. We have seen an increase in NH₄Cl salt formation out of these feeds that can foul the feed-effluent exchangers at higher temperatures. The increase in water formation (up to five times larger than usual hydrocarbon feed) means the possibility of the salts that deposit in the feed-effluent exchangers getting wet increases dramatically. Engineers need to monitor the exchangers for the NH₄Cl formation temperature as well as the relative humidity increase due to increased water content. The engineer should note that at relative humidity greater than 10%, ammonium chloride salts will start to absorb water from the vapour stream. This can cause under- deposit corrosion and pitting in equipment and piping. The equipment most at risk for this type of corrosion is the feed- effluent heat exchangers and the piping up to the reactor effluent air coolers inlet wash water injection. In this case, operations will need to invest in monitoring tools (both software and hardware) that can help them cal - culate salt formation temperatures, water relative humidity, and sour water concentrations (especially bisulphide con- centration) to maintain static asset reliability. Q What role are AI systems expected to play when opti- mising plant-wide operations? A Isabelle Conso, Digital Innovation Director, Isabelle. Conso@axens.net, and Philippe Mege, Digital Services Factory Manager, Philippe.MEGE@axens.net, Axens AI is expected to play a significant role in optimising plant- wide operations. Here are some key roles and benefits that AI systems can provide in this context: u Safety and compliance: AI can monitor safety conditions in the plant and detect anomalies or potential hazards. It can also assist in compliance with regulatory requirements by ensuring that processes and products meet the neces- sary standards. v Process optimisation: AI can continuously analyse vast amounts of data from various sensors to uncover patterns in view of production process optimisation. It can also

produce soft sensors generated through surrogate models that will provide insights for adjustments of parameters such as temperature, pressure, and flow rates to maximise efficiency and product quality. w Predictive maintenance: AI can monitor equipment and machinery in real-time, analysing data from sensors to pre- dict when maintenance is needed. This can help prevent unplanned downtime and reduce maintenance costs. x Production scheduling: AI can create optimised pro - duction schedules that balance production efficiency with demand fluctuations and resource constraints. A Ezequiel Vicent, Senior Application Engineer and Consulting Lead, OLI Systems AI will play a major role in the optimisation of plant-wide operations both during steady-state times and during shut- downs and start-ups. There are many examples of how AI is being used today to optimise a plant, but the decision to go from an open system to a closed system is still a few years away< and the technology has not yet caught up. A prime example of AI being used in plant optimisation is in the area of energy and emissions management. There are energy optimisers that use first principles to look at the current energy status of the unit and are able to optimise fuel consumption and steam production while account- ing for combustion emissions to minimise the amount of energy needed for the steam demand. They will account for steam Cogen units and heat inte- gration. However, to predict future demand, AI models ‘learn’ where the peaks and valleys come in and are able to predict the input changes before they happen. This helps the energy optimiser capture changes more quickly and have additional energy savings. Another area where AI, or in this case a Machine Learning (ML) model, can make a big impact is in dynamic processes, like the start-up or shutdown of a unit. Consider a unit where a process upset occurs upstream, and a column needs to be quickly shut down with a precise sequence of events. The outcome largely relies on the operators’ experience. In such a case, a ML model can be ‘taught’ that exact sequence under varying process and environmental conditions. Various dynamic simulations can be created to show the different types of upsets that can trigger a shutdown, and the shutdown sequence can be included. The ML model, once tested against multiple simulations, can now be added as a closed-loop system and allowed to ‘operate’ the shutdown or start-up of the column to avoid damage to the unit or unwanted chemical releases. However, for more complex systems, AI still needs to evolve as a technology. Several refiners we have worked with have started on the path of AI implementation but have stopped short of full ‘autonomous plant’ systems. We have heard that the complexity of the processes at the refinery and the constant variation of feedstock and pricing have made it difficult to gain value from full AI implementation. A Lisa Krumpholz, CSO, Navigance GmbH, Lisa. Krumpholz@clariant.com The major challenges of optimising plant-wide operations

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A Johanna Fernengel, Product Manager, Syngas and Fuels, Johanna.Fernengel@clariant.com, and Rainer Albert Rakoczy, Technology Advisor Fuel and Hydrocarbons, Syngas and Fuels, Rainer.Rakoczy@clariant.com , Clariant Catalysts Besides topping upgrading, the key to maximising fuel pro- duction is the right balance of hydrocracking (HC), delayed coking (DC), and catalytic cracking (FCC), as this gives the highest flexibility in utilising nearly any crude source, including renewable sources. In particular, utilisation of the light olefins from the FCC off-gas with alkylation and oligo - merisation with alternative concepts can give a higher flex - ibility, moving from sole gasoline focus towards distillates as potential diesel and jet blending components. A Ioan-Teodor Trotus, Team Leader Refining, Ioan- Teodor.Trotus@hte-company.de, hte GmbH Which reactor system will be the most effective depends on multiple factors, such as the feed or feed mix to be con- verted, the actual fuel to be produced – diesel, gasoline, or aviation fuel – and, of course, on which reactors are already operating in the refinery. For a refinery that aims to convert mainly crude oil with existing plants – be it hydrotreaters, hydrocrackers or FCC units – pilot plant tests will yield the most reliable results for choosing the right catalyst system. The right catalyst system must show a reasonable level of activity and stability to maximise the duration of an operating cycle. This can be determined in pilot plant testing either as the start-of-run activity or by performing accelerated deacti- vation studies to estimate the mid-run or end-of-run activity. At the same time, pilot plant testing will give information about the yields and properties of each fuel fraction, allow- ing one to feed a techno-economic model with actual plant data and make a like-for-like comparison of all the catalyst systems to be compared. For a refinery aiming to co-process or process renewable feedstocks in existing equipment, a pilot plant test is even more important because it also allows the operator to see a new application in action before testing in a production unit. The number of industrial references for the conversion of renewable fuels is still relatively low compared to the num- ber of references for the conversion of crude-derived feeds. Simply relying on models and paper studies is particularly risky in these cases, as such models still have relatively little data on which to build their estimates. In short, the most effective catalyst – be it for hydropro- cessing or FCC applications aimed at the production of fuels and the conversion of renewables – will most likely be the one that was determined by a pilot plant test. A Kurt du Mong, CEO, Zeopore Technologies A key value creator in the refinery, specifically to yield fuels, remains the hydrocracker. These units feature multicom- ponent catalysts involving NiW or NiMo hydrogenation components supported on acidic zeolite/alumina carriers. These types of catalysts have gone through generations of remarkable developments, particularly with respect to the optimisation of the zeolite component.

are the vast amount of data available and the high com- plexity of interconnected unit operations. Traditional first-principles models and tools for optimisation have dis - advantages in coping with these challenges as they usually require high effort and thus cost to develop, maintain, and adapt to changes in the operation. In contrast, AI systems with machine learning-based models at their core can be designed with reasonable effort for complex systems. They offer the opportunity to learn automatically from continuous data streams in the plant and adapt quickly to changing conditions. Thus, AI systems will see rapid adoption in the coming years to replace, complement or enhance existing optimi- sation approaches. Like the developments in autonomous driving, AI systems are expected first to be adopted as assisting systems to support and enable better human decision-making for plant-wide optimisation. Q Gasoline, diesel, and aviation fuel are still expected to dominate refinery markets to 2030; what reactor and catalyst systems will be the most effective in maximising fuel production? A Pierre-Yves le-Goff, Global Market Manager Reforming and Isomerisation, Pierre-Yves.LE-GOFF@axens.net, Laurent Watripont, Clean Fuels Technologies Director Expert, Laurent.WATRIPONT@axens.net, Christophe Pierre, Reforming Product Line Manager, Gasoline Product Line Technology and Technical Support Business Division, Christophe.PIERRE@axens.net, Matthew Hutchinson, Senior Technology Manager, Gasoline and Petrochemical Technologies, Technology Dept., Matthew. HUTCHINSON@axens.net , Axens For gasoline production, among the building blocks of the gasoline pool, we can mention isomerate and refor- mate. For reforming, maximisation of gasoline production is linked to a reduction of cracking while ensuring a stable operation. The addition of modifiers is one of the possibili - ties to reduce cracking; however, rigorous selection process is needed to ensure that stability and regenerability are not impacted. Axens, formerly Procatalyse, has been involved in such a field of expertise since the mid-1990s. From a process standpoint, reduction of the pressure will improve the fuel production. However, such a reduction needs to be compatible with unit constraints (for example, pressure drop). To mitigate these pressure drops, a pos- sibility is to move from a standard axial flow reactor to a radial flow reactor. Axens has already performed such modifications and has proprietary internals to improve gas distribution. On the isomerisation side, depending on the octane tar- get and feed composition, different schemes can be pro- posed. For example, if the feed is rich in C 6 paraffin, the deisohexaniser (DIH) column can be implemented to maxi- mise octane without selectivity debit. In addition, to reduce cracking, the use of high-activity catalyst is of paramount importance. Therefore, Axens process expertise with ATIS-2L catalyst provides the best combination for isom- erisation unit optimisation.

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PTQ Q1 2024

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Technology Advisor Fuel and Hydrocarbons, Syngas and Fuels, Rainer.Rakoczy@clariant.com, Clariant Catalysts In traditional refining, the catalytic cracker (FCC) is the source for light olefins such as propylene and butylenes. In many countries, demand for gasoline is shrinking as indi- vidual transportation is the most influenced section during the energy transition, moving to lean consumption engines, plug-in hybrids or fully electric-driven solutions. Thus, the product slate behind FCC calls for more distillates and light olefins and less gasoline. Cracking technology providers can offer revamp solutions to follow these requirements (second riser and modified catalyst solution). Clariant can offer adsor - bents and catalysts to clean these streams, delivering high- purity light olefins over the fence or utilising these olefins in the refinery grid toward fuels or even chemicals. A Cai Zeng, Head of PDH Strategic Marketing and Product Management, Propylene Catalysts, Cai.Zeng@ clariant.com, Clariant Catalysts Petrochemicals customers are now looking for unique and extremely reliable technology for co-processing butane and propane to meet both increasing butylene production and propylene demand. Catalysts such as Clariant’s highly selective Catofin catalyst and the company’s patented metal-oxide HGM allow for thermodynamically advantaged reactor pressure and temperature to achieve a high conver- sion rate and maximised yield. One example is the Hengli Group’s world’s largest mixed-feed dehydrogenation plant in China using the Catofin technology. The plant is designed to process 500 KTA of propane and 800 KTA of iso-butane feeds to produce propylene and iso-butylene. A Kandasamy Sundaram, Distinguished Technologist & Lummus Fellow, kandasamy.sundaram@lummustech.com On-purpose propylene routes are satisfying the demand to some extent. FCC and olefin conversion technology satisfy some additional capacity in addition to thermal cracking. Butene-1, Butene-2, and isobutene have different markets. Due to the decline in the MTBE market, isobutene is not requested by our clients. The dimerisation of ethylene is meeting some demand. A Victor Batarseh and Bani Cipriano, W. R. Grace & Co. The FCC unit is a key source of both propylene and butyl- ene. While the primary drivers for propylene and butylene demand are different, there is some overlap in the fac- tors that influence their production in the FCC. Propylene demand stems mostly from the demand for polypropylene and other chemicals such as acrylonitrile and cumene. Meanwhile, butylene demand primarily stems from the pro- duction of high-octane alkylate used as a blending stock for gasoline. The FCC can produce high amounts of propyl - ene and butylene, and to increase their production, refiners have process knobs available such as feedstock selection, implementation of FCC product recycles, adjustment of cat-to-oil ratio, and hydrocarbon partial pressure (among others). At times, the knobs previously listed are not sufficient to bring refiners to a truly optimised yield slate with respect to

Over the last decade, it has become clear that optimis- ing the zeolite’s mesoporosity and macroporosity enables the control of the degree of cracking, thereby maximising the yield of fuels, which was demonstrated in a selection of refineries. However, thus far, mesoporous zeolite-based hydrocracking catalysts have been associated with inhibi- tive cost increases and lower conversion levels, limiting their widespread application. Zeopore helps to overcome such limitations via a platform of affordable USY zeolites, yielding selectivity and activ- ity benefits of a wide range of catalyst types and zeolite contents. Zeopore’s mesoporised hydrocracking zeolites have recently been tested in a high throughput facility of a major refiner, generating up to 4 wt% more middle dis - tillates at retained activity levels, generating $15 million more profit per average hydrocracker (see Zeopore press release: www.zeopore.com/post/zeopore-enables-break - through-in-hydrocracking-by-leveraging-zeolite-meso- pore-quality) Q How is the dual focus on increasing butylene and pro- pylene production being met? A Alvin Chen, Global Technology Application Manager, Hernando Salgado, Technical Service Manager, BASF While butylene pricing is often quite stable (typically either very high or very low), propylene pricing has seen signifi - cant volatility over the past few years. One approach that many refiners have adopted, to address the dual focus on butylene and propylene production, is to formulate a base FCC catalyst with moderate overall LPG= selectivity and an emphasis on strong C₄= selectivity. Such a catalyst coupled with judicious usage of ZSM-5 offers excellent C₄= selec - tivity during times when C₃= value is low. However, it still allows the refiner to capture short-term C₃= opportunities while maintaining a strong C 4= yield. One strategy for the optimum base catalyst is to optimise the acid site distribution on the catalyst by increasing total surface area while reducing acid site density, allowing simi- lar catalytic activity with reduced hydrogen transfer. Since it is known that butylenes are more sensitive than propylene to hydrogen transfer effects, a catalyst with this approach will target both products depending on process conditions and externally added ZSM-5. BASF applies this catalyst design approach in the Multiple Frameworks Topologies (MFT) technology, where secondary zeolite frameworks are also used to further improve butylenes to propylene flex - ibility. Catalysts like Fourte and Fourtune for VGO applica - tions and Fortitude for resid applications are examples of the MFT catalyst technology for FCC units. It should not be forgotten that operating conditions, such as catalyst-to-oil ratio and reactor outlet temperature, also have an impact on butylenes to propylene distribution, with butylenes favoured at mild severity conditions, while pro- pylene is favoured at high severity conditions. A Stefan Jäger, Applied Catalyst Technology Engineer, Stefan.Jaeger@clariant.com, Rainer Albert Rakoczy,

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PTQ Q1 2024

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C= Yield vs. Conversion

C= Yield vs. Conversion

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Figure 1 Yield shifts from an FCC implementing GBA, where the FCC observed increased butylene and propylene yields of approximately 1 vol% at equivalent conversion levels

propylene and butylene production. In this case, collabora- tion with the FCC catalyst partner is required to evaluate catalytic solutions that bring another degree of freedom to solving this challenge. To target increased LPG olefin production, it is important to ensure the FCC base catalyst drives appropriate levels of gasoline yield and olefinicity. The resulting gasoline olefins are then cracked into smaller LPG olefins via the incorporation of a pentasil zeo - lite technology. While this overall approach holds for both propylene and butylene, the choice of catalyst and pentasil technology can influence whether butylene or propylene selectivity is maximised, as will be explained in more detail. Butylene Grace’s approach to increasing butylene yields is two- fold. Starting with a base catalyst that supplies sufficient conversion and gasoline olefinicity is key. Building on that foundation, Grace supports customers with both additive- based and catalyst-oriented solutions. For refiners who

require flexibility to quickly manipulate butylene yields with the backdrop of shifting constraints or feedstock avail - ability, an additive solution is recommended. GBA can be implemented to quickly increase butylene without as much propylene increase as a traditional ZSM-5 additive. Figure 1 shows yield shifts from an FCC implementing GBA, where the FCC observed increased butylene and propylene yields of approximately 1 vol% at equivalent conversion levels. When refiners consistently require higher butylene yields, Grace considers adjustments to base catalyst formulation to incorporate both Y and pentasil zeolites with its proprietary Achieve 400 platform of catalyst, which delivers impressive butylene yields and selectivity. Incorporating the pentasil zeolite functionality directly into the base catalyst with optimised active-matrix surface area, zeolite-to-matrix surface area ratio, pore distribution, and Y-zeolite stabilisation maximise butylene yield and selectivity while also improving gasoline octane and LPG olefinicity. Achieve 400 Prime is the latest development on the butylene selective catalyst platform and delivers the highest butylene yields, selectivity, and LPG olefinicity. Figure 2 demonstrates the step-out butylene yield and selectivity performance of Achieve 400 Prime relative to competitor butylene selective catalyst. Propylene As in the case of butylene maximisation catalyst systems, when selecting a catalyst for maximising propylene, the need for conversion is balanced against minimising hydro- gen transfer reactions to preserve gasoline-range olefins. Traditionally, to minimise hydrogen transfer, max propylene catalysts are designed with low unit cell size and a coke- selective matrix. Max propylene catalyst systems include a ZSM-5 technology that cracks gasoline olefins into LPG ole - fins while shifting the selectivity towards propylene. FCCs with a high propylene yield of 11 wt% or higher are not uncommon. In these cases, a high addition rate of ZSM-5 is used. Relative to a lower activity ZSM-5 additive, using the

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Figure 2 Butylene yield and selectivity performance of Achieve 400 Prime relative to competitor butylene selective catalyst

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PTQ Q1 2024

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highest activity ZSM-5 results in reduced additive con- sumption for a similar or higher propylene yield. Since ZSM-5 can only crack gasoline-range molecules, using a large amount of ZSM-5 additive results in a dilution of the base catalyst activity and lower conversion of feed- stock into gasoline olefin precursors. The main benefit then of using a high-activity additive is to minimise the dilution of the base catalyst activity vs the use of a lower- activity ZSM-5 additive. To maximise propylene, Grace recommends using high-activity ZSM-5 additives from its OlefinsUltra family of additives or its newest innovation in ZSM-5 technology, Zavanti additives. In summary, refiners are adopting a variety of strate - gies to increase butylene and propylene from the FCC, depending on their specific hardware constraints, down - stream handling limits, and regional economics. FCC cata- lysts and additives are key elements of the strategy as well, given the flexibility they offer and the dynamic nature of the FCC unit operation. A Ezequiel Vicent, Senior Application Engineer and Consulting Lead, OLI Systems The dual focus on increasing butylene production and pro - pylene production is being met with ZSM-5 technology and a propane/propylene (PP) splitter (50-300 MMUSD). Refiners on the US West Coast and the Gulf of Mexico are best positioned to take advantage of an increase in the production of butylene and propylene. However, market

drivers and asset characteristics will dictate the extent of the benefit realised. Increasing the production of propane, propylene, and butylene can be achieved by introducing additives to the FCC catalyst, the zeolite ZSM-5. This ZSM-5 will help in the cracking and production of butylene and propylene. The butylene will be used at the alkylation (sulphuric or HF acid) unit to produce alkylate, a gasoline-range material almost void of contaminants and aromatic components and makes an excellent blending component in the gaso - line pool. Whenever there is insufficient butylene or a market need for increased alkylate, propylene can also be added to the alkylation unit. However, the propylene can be cleaned at a PP split- ter and further refined to either chemical-grade propylene (92-95 mass% propylene) or polymer-grade propylene (99.5 mass% and greater). If a refinery does not have a PP splitter as an asset, the butylene/propylene or propane/propylene mix can be sent to the gas plant and recovered as ‘refinery gas’, which can be later used as fuel to the various furnaces in the refinery. The investment to design and install a PP splitter at a refin - ery is not small. Pre-C OVID estimates put the total cost of the project at around 300 million US dollars (2019) on the West Coast (California) and around 50 to 100 million US dol - lars (2019) in the Gulf. The three-to-one ratio difference is due to labour and materials costs on the West Coast.

13

PTQ Q1 2024

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