catalysis ptq 2024
FULL CYCLE CATALYST MANAGEMENT RENEWABLES CO-PROCESSING
WASTE PLASTICS UPGRADING HYDROCRACKING TO SAF
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PTQ supplement
catalysis ptq
3 Resiliency of fossil-based feedstocks Rene Gonzalez
2024 www.digitalrefining.com
5 catalysisq&a
15 Incorporating new technology and tools for catalyst development Rene Gonzalez PTQ 21 FCC co-processing of biogenic and recyclable feedstocks: Part I Jon Strohm, Darrell Rainer, Oscar Oyola-Rivera and Clifford Avery Ketjen 31 Passivating vanadium in FCC operations Corbett Senter, David M Stockwell, Bingliang Liu and Benjamin O’Berry BASF 35 Hybrid catalyst loading reduces fill cost and carbon footprint Steve Mayo Eurecat 40 Catalyst rejuvenation offers circular solution for hydroprocessing catalysts Jignesh Fifadara and Madeline Green Evonik 44 Catalyst technology for maximum light olefins and ultra-low emissions Ray Fletcher Gasolfin 51 Experimental study on diesel fuel haziness Dhiraj Gondalia, Murthy Nelakanti, Kinjal Patel and Shailesh Gadhvi Nayara Energy Ltd Research & Development Centre 57 Troubleshooting low or high regenerator temperatures Warren Letzsch Refining and FCC Consultant
61 Zeopore is making its mark in green applications through zeolite modification
Cover: The industry is building more new refining capacity, not less, in the trend towards repositioning of assets. Courtesy: Patrick Schatz, Unsplash
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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.
Resiliency of fossil-based feedstocks W ith growing scepticism surrounding the future viability of electric vehicles, it stands to reason that peak fuel projections need to be extended beyond 2030. That will not stop refiners seeking to capture higher margin value through conversion of a wide range of petrochemicals. However, it seems that the demand for and production of transportation fuels will remain strong going into the next decade. The industry still benefits from investing in fuel diversity, including alternative feedstocks from biomass-derived materials, making catalytic upgrading essential, such as the onus on increasing sustainable aviation fuel (SAF). For example, the Preem Lysekil refinery is upgrading its hydroc rack ing unit to increase SAF production by up to 1.2 million cubic metres per year (22,000 bpd) using Topsoe’s proprietary HydroFlex technology. One trend we see is that the economics of upgrading resid through the FCC are still strong. In a recent comment to the trade press, Dr Bani Cipriano, FCC Segment Marketing Manager at Grace, explained, “Our customers are taking advantage of this trend, processing heavier, higher metal laden feeds.” He added: “Using generic eco- nomics, in one trial we estimated use of PARAGON catalyst resulted in $0.65/bbl of value delivery which translates into $14MM per year for an average size FCC.” Researchers are developing catalysts tailored for the unique properties of bio- based feedstocks, contributing to the integration of renewable resources into tra- ditional refining and petrochemical processes. Investors are channelling significant capital into a wider range of renewable fuels. This includes the hydrogen sector, where several technology licensors are pushing forward with liquid organic hydro- gen carrier (LOHC) technology. In parallel with increased blue or green hydrogen production, scale-up is facilitated by LOHC technology that can efficiently transport hydrogen from a steam methane reforming (SMR) unit (for example) and into storage and pipeline networks for inte- gration with existing transportation and refinery infrastructure. However, there is still uncertainty about these future fuels, such as a relatively small group’s ability to deny a permit for a proposed Enbridge ammonia plant in Ingleside, Texas, influenced by a recent oil spill in the area. This is a good example of how an environmental incident in one sector of the energy industry (oil and gas) can affect the viability of an emerging sector, such as natural gas-based ammonia and hydrogen. Whether the US Administration’s decision to halt natural gas/LNG projects will affect investment in new hydrogen-related projects is cause for concern. Nonetheless, there are drawbacks to these bespoke technologies. For example, the use of toluene and other hydrocarbon-based carriers as a hydrogen carrier in LOHC technology may hinder permits. The potential for bio-based carriers for the hydrogenation and dehydrogenation phases of the process may eventually be developed. Furthermore, electrolysis-based technology for green hydrogen solu- tions is expected to be more expensive than blue or grey hydrogen production beyond 2030, at a time when the industry is keenly focused on cash preservation. It is no secret that sustainability must be on par with profitability. For exam - ple, with the industry’s dual focus on producing zero-emissions fuels and emis- sions control from major refinery conversion units, improved sustainability can be achieved with a wider operating window. FCC additives for emissions and regen- erator control can increase catalyst activity and efficiency, such as with the use of additives with more durable precious metals via support surface morphology, as will be discussed in the following pages of Catalysis 2024 .
catalysis ptq
2024
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catalysis q&a
More answers to these questions can be found at www.digitalrefining.com/qanda
Q How are catalyst suppliers further enhancing catalyst formulations for refiners focused on processing a wider array of feedstocks (such as renewables, plastic waste, and heavy crudes)? A Benoit Durupt, Global Market Manager Hydro- processing, Axens, benoit.durupt@axens.net Reaching the ambitious objective of producing more sus- tainable fuels or petrochemical products is a big challenge for all players in the oil industry. It involves processing new types of feedstocks with a wide range of properties. To be viable, this evolution needs to rely on exist- ing assets and reliable, flexible, and proven processes. Hydroprocessing is an appropriate example of this kind of technology, which operators can have confidence in due to its 70 years of existence. It is used in almost every refinery in the world to treat a range of feedstocks to meet the fol- lowing objectives: • Producing sustainable aviation fuel (SAF) or hydrotreated vegetable oil (HVO) through co-processing or a hydropro- cessed esters and fatty acids (HEFA) process such as the proprietary Vegan technology, processing various types of lipidic feedstocks. • Performing chemical recycling of plastics through co- processing or the proprietary Rewind Mix process. Axens has provided more than 300 licences and several hundred thousand tons of top-ranked hydroprocessing catalysts throughout the years, as well as high-standard technical services. The recent launch of a dedicated cata- lyst series (700 series) is designed to ensure reliable pro- cessing of renewable feedstocks with the highest yields of SAF and HVO during long cycles, either in co-processing or dedicated units. The 700 series also contains dedicated products for processing pyoils from waste plastics, allow- ing its smooth re-incorporation in a steam cracker without any detrimental impact on operation. Overall, significant work has been done on the support and active phase of the catalysts to take into account all the specificities of those new feedstocks while maintaining the highest flexibility of the global catalytic system. Minimising the environmental impact of our catalysts is essential. As a consequence, sustainability is one pillar of the development of the 700 series, with a particular focus on: • Outstanding activity and stability during the operation to minimise the need for catalyst replacement. • Full regenerability and rejuvenability through the proprie- tary Revival process to recover up to 95% of its activity after a full operating cycle, thus minimising consumption of metals and minerals required for new catalysts. A Guillaume Vincent, Technology Manager, BASF Refining Catalysts Both renewable or opportunistic feedstocks are being con- sidered by refiners to meet their environmental goals (for
example, Scope 3 emission reduction) or increase their profitability, respectively. Typically, these renewable feed - stocks, such as pyoils from waste plastics or biomass, can have a significant amount of metal poisons, such as alkali (for example, Na, K) and earth alkaline metals (for exam- ple, Ca, Mg). In addition, chlorides and oxygen-containing molecules might be present in these renewable feedstocks depending on the raw materials used during the thermo- chemical conversion process. Opportunistic feedstocks are typically cheaper but often have poorer qualities (such as high metal contents and lower API). Most often, these opportunistic feedstocks are associated with higher metal poison contents, such as nickel, vanadium, iron, and some others, as well as higher Conradson Carbon Residue (CCR) content, which might result in faster catalyst deactivation compared to conventional vacuum gas oil (VGO) or resid feedstocks. One important aspect to consider for the catalyst itself is how the pore structure of the base catalyst will handle such renewable or opportunistic feedstocks. The manufacturing process for fluid catalytic cracking (FCC) catalysts devel - oped by BASF is a big advantage compared to incorporated technologies when dealing with a wider array of feed- stocks. The in-situ technology brings the following benefits from the manufacturing process itself, such as: • Maximum surface porosity provides better tolerance against iron poisoning with respect to incorporated catalysts. • Maximum zeolite surface area to maximise coke-selective cracking activity. • The in-situ technology does not use any chloride-based binders during the manufacturing process, avoiding the introduction of chlorides into the FCC unit. This reduces corrosion and fouling issues (such as NH₄Cl deposits). • The lowest FCC catalyst sodium content in the industry improves catalyst activity retention. Chlorides present in pyoils from plastics and biomass are typically not detrimental to the FCC catalyst. However, an in-situ technology will help minimise the introduction of chlorides into FCC operations from the catalyst. Chlorides are known to reactivate the nickel already deposited at the catalyst edges, resulting in further coke and hydro- gen make. Consequently, nickel and vanadium passivation technologies might be incorporated into the catalyst for- mulation to passivate nickel and vanadium to minimise hydrogen and coke make when chlorides are present in the feedstock. For renewable feedstocks, such as pyoils from plastics and biomass, alkali and earth alkaline metals will neutralise the acid sites of the zeolite, resulting in catalytic activity deple- tion. Consequently, new passivation technologies tailored for biogenic and circular feedstocks are being studied and developed to upgrade these alternative feedstocks further while maximising activity maintenance. Additionally, the
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neutralisation of the acid sites by alkali and earth alkaline metals can be better mitigated using a low-sodium content catalyst, such as in-situ manufactured catalysts. Vanadium passivation technology (for example, Valor) might also be needed to minimise the affinity that vanadium might have with alkali metals (such as Na and K) for better activity maintenance. Oxygen-containing molecules present in biogenic feed- stocks will also induce the optimisation of the catalytic sites to manage the deoxygenation reactions that are inevitable through FCC reactions. These reactions typically include dehydration (oxygen lost as H₂O), decarbonylation (oxygen lost as H₂O and CO), and decarboxylation (oxygen lost as CO₂). If these deoxygenation pathways are uncontrolled, this can result in higher coke make and lower biogenic carbon recovery. The FCC catalysts must be fine-tuned to minimise biogenic coke formation and maximise biogenic carbon recovery in the valuable products while minimising hydrogen loss from products (for example, retaining the H/C ratio). For opportunistic feedstocks, technologies increasing the diffusion and conversion of large molecules for bottoms upgrading while producing less coke and dry gas will be required. Higher meso-macro porosity and better pore con- nectivity between the matrix and the zeolite will help con- vert these large molecules. Enhanced nickel and vanadium passivation technologies will help produce less coke and dry gas while enhancing activity maintenance to produce more valuable products. Improved bottoms cracking activ - ity and selectivity to coke is achieved by optimising matrix properties: Optimal acidity to maintain bottoms cracking while min- imising coke selectivity. Optimal surface area to provide enough active sites. Sufficient pore size distribution to ensure accessibility to catalyst surface. A Andrea Battiston, Global Business Advisor, andrea.bat- tiston@ketjen.com, Jaap Bergwerff, Business Development Director Renewables, jaap.bergwerff@ketjen.com, Stefano Melis, Global Hydroprocessing Specialist, stefano.melis@ ketjen.com, Ketjen The energy transition is compelling refiners to process more renewable and recyclable feedstocks like vegetable oil and waste plastic oils (WPOs) for production of transportation fuels and chemicals. These feedstocks present new chal- lenges for the hydrotreating catalyst systems, necessitat- ing enhanced formulations and new ways to apply them in commercial practice. These challenges can be summarised into three main types, each demanding a distinct approach and solution. Inorganic impurities Firstly, the new feedstocks can contain inorganic impurities not present in fossil feedstocks or in different concentration and molecular forms. Removal of the impurities by means of reaction and deposition in the guard catalyst section is required to prevent contamination and deactivation of the main catalyst. The case of phosphorus (P) and metals
trapping is the most common challenge and illustrates how catalyst systems are being improved. P-containing mol- ecules present in fossil-spent lube streams are generally highly reactive. In contrast, the phospholipids prominent in animal fats, for instance, are highly reactive and bulky. As a result, the guard bed catalyst must provide the right balance between its active sites’ accessibility, pore volume storage capacity, and active phase activity. In this way, the maximum amount of phosphorous and metals can be reacted and trapped in the whole catalyst pore volume and not just in the proximity of its external surface. In WPOs phosphorous is present as the remnants of P-containing flame retardants alongside a broad range of, sometimes exotic, elements and metals that one would not find in any other feedstock. The guard catalyst, in this case, needs to be tailored to trap all these elements. Note that for waste plastics hydrotreating, there are large dif- ferences in the pretreatment and the trapping strategy depending on the source of the plastics, be it olefins or aromatics. Oxygenates A second challenge arises from the presence of oxygenates in non-fossil feedstocks, necessitating their removal to meet final product specifications. Once again, the challenges related to removing oxygen depend on the type of feed- stock. Triglycerides contained in vegetable oil and animal fats are readily converted over hydroprocessing catalysts, but the pathway for their decomposition into paraffins can significantly affect the process’s effectiveness. Depending on reaction conditions and catalyst compo- sition, oxygen can be removed via hydrodeoxygenation (HDO), producing water, or via decarbonylation and/or decarboxylation, releasing CO and CO₂, respectively. A high selectivity towards the HDO pathway is generally desired as it maximises the hydrocarbon product yield and, where applicable, prevents downstream catalyst poisoning by CO. For example, when renewable feedstock is co-processed with fossil fuel, CO inhibits the hydrogenolysis reaction pathway to remove suphur, impacting the performance of hydrotreaters loaded with CoMo catalyst, which are typi- cally those operating at low hydrogen pressure. For HDO, selection of the active metals in hydrotreating catalyst formulation is key to balancing the hydrogenolysis and hydrogenation functions. In addition, HDO catalysts need to be accessible to large molecules (triglycerides) and capable of tolerating metal slip from the metal trapping lay- ers above the reaction zone, which can occur later in the operating cycle, so excellent pore accessibility remains a key property throughout the cycle. This explains why HDO catalysts also require an open pore structure. Note that in bio-oils obtained by liquefaction of biomass sources such as lignocellulose, oxygen concen- trations are very significant. The extremely high reactivity of some of the oxygenates can result in stability and han- dling issues, so a stabilisation step at low temperature with a catalyst with a specific composition is applied prior to regular hydrotreating.
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Flexibility is profitable
Flexibility Matters
tray vapor loads and internal liquid reflux rates. Keeping the upper pumparounds loaded can also help avoid low pumparound return or tower overhead temperatures that condense water and cause salting or corrosion problems. It may even make sense to turn off a lower pumparound. L ONG - TERM SOLUTIONS inking longer-term, cost-effective revamps can add critical flexibility to allow for wide swings in unit throughput and crude blends while still operating in control. e right process design enables operators to consistently:
In uncertain times, refineries can maximize profit (or at least minimize loss) through flexible operations. Crude units are the first link in the refinery processing chain, and making large changes in crude diet or throughput stresses even the most state-of-the-art unit. S HORT - TERM STRATEGIES Certain operating strategies can maximize reliability, yields, and product qualities. Some practical short- term options include: • K EEP THE BOTTOMS STRIPPING STEAM
At turndown, consider maintaining normal crude tower and vacuum tower bottoms stripping steam rates and lowering heater outlet temperature to control cutpoint. is allows the stripping steam to do the work while heater firing is minimized to protect the heater tubes at low mass velocities. L OWER THE PRESSURE Lowering tower pressures at turndown lowers the density of the vapor, which keeps trays loaded and can avoid weeping and loss of efficiency. Lower pressure also lowers draw temperatures, increasing pumparound rates and hopefully avoiding minimum flow limits for pumps and tower internals. M OVE HEAT UP In multi-pumparound towers, shifting heat to the upper pumparounds at turndown increases
•
Control desalter inlet temperature,
• Control preflash column inlet temperature and naphtha production, • Control pumparound return temperatures and rates independent of pumparound heat removal requirements, and • Precisely control vacuum column top pressure. is advice is, of course, generic. To discuss challenges unique to your own crude/vacuum unit, give us a call. Process Consulting Services believes crude units should have flexibility. We believe that revamp solutions should be flexible too - one size doesn’t fit all. We look forward to working together to find the most cost-effective and reliable solution to your crude processing problems.
•
•
3400 Bissonnet St. Suite 130 Houston, TX 77005, USA
+1 (713) 665-7046 info@revamps.com www.revamps.com
Fossil oil fraction
Waste plastics oil
Figure 1 Speciation of neutral N-containing compounds as measured in a fossil oil fraction (left) and a waste plastics oil (right) via N-selective GCxGC, showing the absence of carbazoles and other refractory compounds in this waste plastics oil
Nitrogen-containing compounds Thirdly, as is the case of fossil feedstock hydroprocessing, and with renewable and recycled feedstocks, the pres- ence of nitrogen-containing compounds can negatively affect overall hydroprocessing catalyst system perfor- mance; hence, a catalyst load with proper hydrodenitro- genation (HDN) activity is required. To produce renewable diesel or sustainable aviation fuel (SAF) via the hydropro- cessed esters and fatty acids (HEFA) route, nitrogen must be removed to prevent deactivation of the downstream hydroisomerisation catalyst. Especially when animal fats are processed, the feedstock is rich in nitrogen, which is difficult to convert, as in the case of tertiary amides. To handle these large refractory molecules, a specific cat - alyst is required with high HDN and hydrogenation activ- ity, and excellent pore accessibility. On the other hand, in WPOs, the total nitrogen content can occasionally be high, typically consisting of easy, neutral species, with only negli- gible amounts of refractory compounds like carbazoles (see Figure 1 above). In summary, effective hydroprocessing of renewable and recycled feedstocks demands tailored catalyst formulations and loading configurations, informed by a comprehensive understanding of feedstock molecular composition and
reactivity, as well as catalyst functionalities. This requires extensive specific work in the lab and on the commer - cial units. Collaboration between process operators and catalyst suppliers, leveraging decades of experience, is essential. The proprietary ReNewFine catalyst solutions developed through a decade-long partnership between Ketjen and Neste, and applied using Ketjen’s proprietary ReNewSTAX catalyst loading strategy exemplify the suc- cess of this collaborative approach in producing renewable diesel and sustainable aviation fuel. A Victor Batarseh , Strategic Marketing Manager, FCC, victor.bataresh@grace.com , Stefan Brandt , FCC Market Development Director, Energy Transition, Stefan.brandt@ grace.com, W. R. Grace & Co. Grace’s catalyst technologies have been enhancing the prof- itability of FCCs for more than 80 years. Most of the efforts have been focused on catalyst technologies that unlock increased feedstock flexibility for refiners while maintaining a targeted yield slate for maximum profitability. Significant advancements in catalyst technology have optimised oper- ation while maximising high boiling point, aromatic, highly contaminated resid feedstocks. Grace’s approach (see Figure 1 below) to providing catalytic solutions involves a
Mesoporosity Hydrothermal stability Acidity Acid site density Na tolerance Content
Heat capacity Physical strength
Clay
Zeolite Y
Attrition resistance Bottoms cracking
Bottoms cracking
Binder
Mesoporosity Macroporosity Type Content
Ni tolerance V tolerance Fe tolerance
Metals tolerance
Matrix
FCC Catalyst Design
Mesoporosity Macroporosity Content
Mesoporosity Macroporosity Particle size distribution Sphericity Hydrothermal stability Attrition resistance
Hydrothermal stability Acidity Acid site density Content
Processing
Pentasil
Figure 1 FCC catalyst design factors
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110%
70
Ni, mg/kg V, mg/kg Fe, wt%
Continuous Tria l led Interested
60
105%
50
40
100%
30
20
95%
10
90%
0
2016
2019
2023
2021
2022
2023
Figure 2 Summary of Ecat contaminant trends
Figure 3 Interest in FCC co-processing
multi-pronged strategy employing specialty technologies and production processes to tune the zeolite stability and activity, catalyst porosity, matrix activity, and tolerance to contaminant poisons within the relatively strict property window for optimum fluidisation and in-unit retention. As refiners continue pushing the envelope on feedstock flexibility, it is important to implement catalyst technologies that mitigate the harmful effects of contaminant metals on performance. An analysis of Grace’s Ecat database, shown in Figure 2 , indicates refiners are processing increased amounts of opportunity feedstocks laden with iron and vanadium. In concert with these trends, Grace has recently unveiled two proprietary catalyst technologies, Midas Pro and Paragon catalysts. Built on the Midas platform, Midas Pro catalyst has been proven commercially to provide a baseline iron tolerance improvement, as well as a barrier to unexpected feed iron excursions in the FCC. Midas Pro catalyst improves iron tolerance through optimisation of matrix surface area and pore distribution. The proprietary Paragon catalyst is the culmination of significant R&D and manufacturing investment, applying vanadium trapping technology to the Midas platform, offering a synergistic effect for conventional metals trapping and iron tolerance. In addition to processing more challenging petroleum feedstocks, Grace has observed a steep increase from the industry in co-processing alternative feedstocks, including bio-based renewables and plastic waste oils (see Figure 3 ). These unconventional feedstocks pose new opportunities and challenges for the refining industry, and we are actively collaborating with refiners to minimise the risks and maxi - mise the value associated with such feeds. Our extensive testing facilities are instrumental in provid- ing our customers with an understanding of these uncon- ventional feedstocks. Detailed feedstock analysis, ACE unit testing, and circulating riser pilot plant testing are utilised to identify and mitigate challenges and operability con- cerns. Following these evaluations, refiners can more con - fidently engage in commercial FCC trials and continuous co-processing while implementing catalyst reformulations to maintain optimal operation. These unconventional feedstocks are often accompanied by contaminants and heteroatoms, which are not present in fossil feeds. The contaminants of interest vary significantly
by feed source but can be categorised as surface contami- nants and zeolite deactivators. This requires a deep under - standing of fluid catalytic cracking and catalyst technology to pioneer solutions that tackle the unique challenges posed by the unconventional contaminants in the next generation of feedstocks. These alternative feedstocks can also contain significant amounts of oxygen. Pilot plant and commercial observa - tions suggest that most of this oxygen is converted to water, CO, and CO 2 , which can pose challenges with water handling and amine scrubber systems. However, even trace amounts of oxygenates in sour water systems and LPG products can cause significant challenges downstream from the FCC. Grace’s proprietary Oxyburn additive represents the first step on a catalytic journey to reduce FCC product oxygenates and mitigate issues downstream from the FCC. This enables increased processing of renewable feedstocks in support of refiners’ sustainability goals while also limit - ing the need for capital solutions to address oxygenates. Presently, Grace is providing FCC catalyst and technical support to many FCCs in Europe and the Americas, which are steadily increasing renewable co-processing year over year. Additionally, refiners in the early stages of renewable feedstock co-processing are being supported. Overall, the future of the refining industry remains bright, but it will continue to be shaped by the healthiest and most strategic refiners. FCC operators that invest in technologies to increase feedstock flexibility will be the most resilient through the ongoing energy transition. OXYBURN, MIDAS, MIDAS Pro, and PARAGON are marks of W. R. Grace. Q What AI and data analysis techniques do catalyst and reactor technology developers offer refiners for higher yields while meeting near-zero emissions specifications? A Pierres-Yves Le Goff, Global Market Manager, Reforming & Isomerisation, pierre-yves.le-goff@axens. net and Philippe Mege, Digital Services Factory Manager, philippe.mege@axens.net, Axens AI and data analysis techniques can analyse complex refinery processes to identify optimisation opportunities. They can predict optimal operating conditions and adjust
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parameters in real-time to maximise yields and energy effi - ciency while meeting emissions standards. Here we give several illustrations: • In addition to gasoline and aromatic production from a reformer unit, the other major product is hydrogen. This hydrogen has a low carbon index compared to the one coming from steam methane reforming (SMR) by a factor of around eight. Therefore, any extra hydrogen production is critical. However, to give advice to increase hydrogen production at a first stage, an accurate estimation of the current hydrogen yield is important. This task is not easy as gas flowmeters are not so accurate most of the time. In that context, Axens has developed special tools to accurately follow hydrogen production using in-house data clustering, mass balance closure methodology, and principal compo- nent analysis. Based on hybrid models, first principles and machine learning, new set points can be defined to maxi - mise hydrogen and aromatics production. • Another example is the optimisation of the recycle gas flow rate. Typically, recycle compressors use steam. Consequently, any reduction of the flow has a direct impact on the unit carbon intensity. Again, based on hybrid mod- els, the recycle gas can be reduced to meet either regenera- tor coke burning capacity or the requested cycle length for a semi-regenerative unit. • Multivariable advanced control embedded to advanced process control uses mathematical models to predict the future behaviour of the process and optimise control actions accordingly. This helps in maintaining optimal con- ditions for catalysts and reactors to achieve higher yields while minimising emissions. • Creating digital twins of refining processes allows for simulation and testing of different scenarios without affecting the actual operation. Applied to the aromatics complex, data densification techniques coupled with real- time monitoring enable an aromatic production increase by maximising benzene precursors in the continuous catalyst reforming (CCR) unit inlet. Operational improvements such as octane optimisation in a catalytic reforming process as a function of pool requirement or hydrogen-to-hydrocarbon molar ratio adjustment minimising energy consumption will favour CO₂ emissions reduction. Q With the most profitable refiners focusing on the pro - duction of basic chemicals such as aromatics, olefins, and polyolefins, what catalyst and reactor technology is key to this focus? A Yoeugourthen Hamlaoui, Global Market Manager, Axens, yoeugourthen.hamlaoui@axens.net Modern refineries are divided between those that empha - sise fuel production, particularly gasoline, and those that prioritise the maximisation of petrochemicals output. Petrochemical-centric refineries seek efficient ways to con - vert gasoline into high-value petrochemical products while minimising investments. In this context, Axens has devel- oped several combinations of technologies to help refiners adapt their existing assets. The combined proprietary technology of Prime-G+ and
GT-BTX PluS unveils an avenue for converting gasoline into valuable petrochemical products. In its petrochemical mode with the same configuration, the GT-BTX PluS Extract, a nearly pure aromatic stream with sulphur being the only impurity, undergoes intensified hydrodesulphurisation (HDS) in the Prime-G+ unit, culminating in a high-quality petrochemical benzene, toluene, xylenes (BTX) product. Furthermore, the olefin-rich non-aromatics raffinate stream derived from GT-BTX PluS proves invaluable for FCC recy- cling, producing significantly additional propylene and enhancing the FCC propylene yield. Axens’ FlexEne technology is a low Capex approach that combines two well-established processes: fluidised catalytic cracking (FCC) and oligomerisation. Polynaphtha (awarded the Best Refining Technology 2023 by Gulf Energy Information Excellence) is the Axens oligomerisation tech - nology dedicated to oligomerise olefins contained in the light cracked cut into higher value olefinic cuts, which can be used as high-octane gasoline or high cold properties kerosene or diesel fraction. This combination aims to enhance the capa- bilities of the FCC process, which is typically the main con- version unit in refineries and is generally oriented towards maximising gasoline and, occasionally, propylene production. The innovation in FlexEne lies in its ability to significantly improve the flexibility of product output, allowing for better control over the balance of propylene, gasoline, and diesel production. This flexibility is achieved by selectively oligom - erising light FCC alkenes (olefins) for recycle cracking in the FCC unit. By adjusting catalyst formulations and operating conditions, the FCC process can be adapted to operate in different modes, including the maximisation of propylene. Prime-G+, GT-BTX PluS, GT-BTX PluS Extract, FlexEne, and Polynaphtha are marks of Axens. A Mark Schmalfeld, Global Marketing Manager, BASF Refining Catalysts, mark.schmalfeld@basf.com Over the coming decades, global market demand for refined products is expected to shift. Fewer transportation fuels will be needed (primarily gasoline as the market shifts to electric vehicles) while we see an increased demand for naphtha, olefins, and other petrochemical feedstocks. Also, besides the global trends, each refiner’s profitability can depend heavily on the regional economics, regional product demand, and integration setup to enable the use of petro- chemical feedstocks (internal to the refinery or to supply to local customers). No specific catalyst or reactor technology in the market has emerged as the only option, but there are market- leading processes in use today. Steam cracking is still one of the largest unit operations to produce ethylene and pro- pylene from naphtha. The FCC unit is generally considered the second-largest unit operation to produce propylene. Additionally, we see many processes supporting the market need with a variety of private licensors and governmental licensor designs introduced. These licensor designs include improvements to the FCC unit, modifications to the FCC unit approach (deep catalytic cracking [DCC], HS-FCC, res- idue fluid catalytic cracking unit [RFCC], INDMAX) to shift
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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
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selectivity to chemicals, new integrated refinery design for crude oil to chemicals, steam cracker improvements, and other unit improvements (reforming units, propane dehy - drogenation [PDH] units, methanol-to-olefin processes, and others). Each of these has specific process conditions and/or spe - cific catalysts targeted for the units (from market catalysts to proprietary catalysts, and diverse types of materials/ zeolites – ZSM-5 (MFI), SAPO-34, Beta (BEA) and USY/ REY (FAU) type zeolites) to meet specific refiner’s petro - chemical yield targets. The BASF refinery catalyst team continuously focuses on understanding the new market needs to create technolo- gies to support this transformation to create petrochemical feedstocks from the FCC and other refinery processes. Besides a market demand shift, we are also seeing a shift to using more alternative feedstocks (renewables, pyoils, recycled materials) to reduce the carbon footprint. From an FCC catalyst standpoint, BASF has introduced technologies to address the need for more petrochemical feedstocks (propylene, olefins) and to support the use of alternative feedstocks in these processes. Today, BASF has examples of using FCC catalysts (maximum propylene solution) in commercial units to maximise propylene with both resid, VGO feedstocks and using alternative feed - stocks. Additionally, in North America and the Middle East, we see commercial use of new catalysts (Fourte, Fourtune, Fortitude, and newer materials) to drive both propylene and butylene yields. These catalysts help achieve both chemical and feedstock requirements for alkylation processes, supporting their fuel octane needs. The catalyst technologies needed for maximising petrochemical feed production from FCC units have emerged through rigorous research, development, and technology application improvements. From this work, BASF has found that FCC catalysts require an integrated design approach to the catalyst materials. Use of multiple catalyst zeolite types and different functional materials is essential for the best performance when targeting petro - chemical feedstock production. Additionally, ensuring the flexibility of an FCC unit to accept changes to FCC catalyst formulation or to allow rapid adjustments in olefin additive (ZIP, ZEAL) use enables profit optimisation. Fourte, Fourtune, Fortitude, ZEAL and ZIP are marks of BASF. A Ray Fletcher, Chief Technology Officer, Gasolfin BV, rfletcher@inovacat.com The role of olefins is fundamental to industry today and is the focus of this response. Inovacat believes that this ques - tion is best addressed in three distinct phases. Phase One addresses the immediate future, extending over the next three to five years. Phase Two addresses the medium- range future of the next 15-20 years. Phase Three refers to post-2040 operations. Phase One will be achieved through naphtha and pro - pane conversion assets presently being operated by refiners today, namely FCC and PDH operations for maximum pro - pylene and steam crackers for maximum ethylene. The FCC
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Figure 1 Typical Gasolfin propylene yields
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Figure 2 Typical Gasolfin total olefin yields
propylene yield may be increased via changes to the base catalyst, ZSM-5 additives, and operating the FCC at increased severity. The FCC catalyst may be optimised by reduced rare earth concentrations for reduced hydrogen transfer reactions and with increased zeolite content for activity retention. The PDH unit will require operating at an increased feed rate or debottlenecking. The steam cracker propylene yield is dependent upon the amount of light straight run naphtha (LSR) being charged to the unit. Steam crackers currently feeding LSR to the unit may consider increasing the fresh feed rate by debottlenecking the charge heater. This may be achieved if a portion of the pentane recycle was removed from the feed slate, assuming an alternative outlet for pentane is found. It is believed that most refin - ers intending to begin, or those continuing the transition from fuels to petrochemicals will have already made these changes and so may be limited in the extent of further ole - fin production. Phase Two begins soon and extends for the following 15-20 years. The transition from fuels to petrochemicals is expected to continue with the larger declines observed with gasoline, marginal declines in diesel, and increases in jet fuels.1 At the same time, refiners need to reduce green - house gas (GHG) emissions to achieve 2030/2050 targets. Alternative technologies include options such as high severity FCC, shifts from FCC towards hydrocracking and steam cracking, and many others. Fundamental changes may also be possible with crude-to-chemicals technolo - gies being developed, such as Lummus’ Thermal Crude to
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Chemicals (TC2C) technology. The negative side of these options is the high costs and construction time. Inovacat’s Gasolfin technology fits well into all Phase Two options. The Gasolfin catalyst system converts naphtha boil - ing range molecules into light olefins (ethylene, propylene, and butylene) with total olefin yields up to 88 wt%. Olefin yields are up to 27 wt% ethylene, 46 wt% propylene, and 30 wt% butylene, depending upon feedstock (see Figures 1 and 2 ). The Gasolfin catalyst cracks pentane into 32 wt% pro - pylene. This technology has been under development since 2017 in conjunction with the Chemical Process and Energy Resources Institute (CPERI) laboratory in Thessaloniki, Greece. An alternative outlet for naphtha is expected to be a challenge for profitable refinery operations. Gasolfin is a naphtha conversion technology, producing light olefin with significantly lower CO₂ emissions than the three leading propylene-producing technologies: FCC, steam cracking, and propane dehydrogenation. A paper for benchmarking GHG emissions for existing technologies is entitled Energy and GHG Reductions in the Chemical Industry via Catalytic Processes .² , ³ Gasolfin produces 0.45 tons of CO₂ for every ton of total olefin pro - duced, which is annotated as ‘tCO₂/tHVC’, where tHVC abbreviates ‘ton Highly Valued Chemical’. The HVC defi - nition for Gasolfin is the sum of ethylene, propylene, and butylene. HVC for PDH and FCC is propylene and ethylene for steam cracking. This excellent metric enables a side-by- side comparison of an FCC and a steam cracker. GHG reductions place the GHG emissions of an FCC between 0.783 and 0.869 tCO₂/tHVC. A steam cracker processes naphtha at 0.700 and ethane at 0.964 for an average GHG emissions level of 0.832 tCO₂/tHVC. A PDH unit produces 1.231 tCO₂/tHVC (see Figure 3 ). Inovacat has completed bench-scale and pilot plant test - ing of this technology and is currently finalising the front end engineering design (FEED) study for a demonstration unit to be operated at an Asian refinery. The demonstration plant will start operations in early 2025 to commercialise the technology in 2027. Gasolfin is in fundraising mode to finance this programme up to commercialisation. Phase Three includes post-2040 operations to achieve 2050 targets of net zero emissions and beyond. The technol - ogies currently under development include bio-based olefins via gasification of bio-feedstocks. A disadvantage is that these technologies currently do not always scale well. Another pos - sible route is e-fuels and e-olefins through e-methanol. The advantage is that they scale well but are not yet mature. The profitability of these routes has not yet been proven. The next several decades should prove to be interest - ing in terms of managing the expected declining naphtha demand while continuing to meet the olefin production requirements. We are fortunate to be able to play a role in these critical years to come. References 1 Fitzgibbon T, Simmons T, Szarek G, Varpa, S From Crude Oil to Chemicals: How Refineries Can Adapt to Shifting Demand , McKinsey & Company.
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Figure 3 Comparison with existing technologies
2 Energy and GHG Reductions in the Chemical Industry via Catalytic Processes: Annexes; International Energy Agency, International Council of Chemical Associations, Dechema , 2013, pp17-21. 3 Dziedziak C R, Murphy J J, Olefin production pathways with reduced CO₂ emissions, PTQ Q3 2023 , pp39-47. Q Industry sources project FCC market expansion to more than $8.75 billion by 2030 (vs $6.78 billion today). To what extent is this due to new reactor and catalyst formulations? A Melissa Clough Mastry, Global Director of Technology and Technical Services, BASF Refining Catalysts This question relates to the long-term viability of FCC oper - ations globally. From a catalyst standpoint, it is certain that over the past decade, the innovations brought to market by FCC catalyst vendors have enabled FCC operators to stay profitable and competitive. We have seen many cases where an FCC is prone to be permanently shut down due to either profitability concerns or environmental concerns. Catalyst technology can help or fully alleviate some of those concerns. As an example, environmental regulations in certain parts of the world relating to SOx and particulate matter (including particulate matter composition) can and have been addressed by implementing innovative technologies, specifically by employing an attrition-resistant technol - ogy or simply a technology that does not introduce certain chemicals or elements. In terms of SOx, we have seen suc - cess from refiners and FCC operators who have started to employ or change their SOx additive strategy to put them back into a state of compliance. Certainly, in terms of profitability, this will be a challenge for every refinery, especially those in areas of high market pressure. For this approach, there is no one-size-fits-all answer, and the catalyst solution has to be specially tailored. However, we have seen refiners improve their FCC com - petitiveness by enhancing profitability via pure throughput optimisation (for example, by employing a low delta coke catalyst in a heat-constrained operation) or by shifting the product mix to a more valuable slate (for example, by focus - ing on high-value products, including LPG olefins and/or high octane gasoline).
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THE RENEWFINE CATALYST PORTFOLIO FOR RENEWABLE DIESEL & SAF
Sustainable Solutions, Limitless Potential Ketjen’s ReNewFine Catalyst Portfolio for renewable diesel and sustainable aviation fuel is now commercially available.
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Incorporating new technology and tools for catalyst development
Factors affecting advances in catalyst development benefit from a wide range of expertise
Rene Gonzalez Editor, PTQ
E fficient conversion of fossil-based and renewable feedstocks to fuels and petrochemicals compels better performance from downstream catalytic con- version processes. Improving reactor performance equates to improved catalyst capabilities. Close adherence to the following developments plays a key role in developing and
Zeolite catalysts The zeolite class of crystalline aluminosilicates continues to play a crucial role in refinery and petrochemical catal- ysis. Their shape selectivity allows them to discriminate between molecules based on size and shape. This feature is particularly advantageous in the cracking of hydrocarbons, contributing to increased yields of desired products while minimising unwanted byproducts, such as with the alkyl- ation of butylenes over a zeolite catalyst to meet demand expected to reach 670 thousand tonnes by 2035, com- pared to around 500 thousand tonnes in 2023, according to a ChemAnalyst study. Besides its well-established role as a gasoline octane-enhancing additive, its market value is rapidly extending into areas from solvents to plasticisers, to name a few. Tailoring the pore size and shape of zeolites to match specific hydrocarbon molecules allows for better shape selectivity in catalytic reactions Zeolites’ three-dimensional framework structure of tet- rahedral atoms provides high surface area, acidity, and shape selectivity. Improvements in refinery zeolites aim to enhance their catalytic efficiency, selectivity, and stability. Some areas of improvement include enhanced porosity for more efficient accessibility of reactants to active sites and improved overall catalytic activity. Tailoring the pore size and shape of zeolites to match specific hydrocarbon molecules allows for better shape selectivity in catalytic reactions, improving the efficiency of processes such as isomerisation and FCC. Resid upgrading trends involving the FCC unit benefit from advances in zeolite materials. Just recently, Grace’s FCC Segment Marketing Manager, Dr. Bani Cipriano, said, “One of the trends we see is that the economics of upgrad- ing resid in the FCC are very strong. Our customers are taking advantage of this trend, processing heavier, higher
applying high-performance catalysts: • Sustainable catalyst applications • Zeolite and shape-selective catalysis • Single-atom catalysts • Advancements in hydroprocessing catalysts • Advanced simulation and AI applications. Sustainability
Compared to refinery operations a generation ago, sustain- ability is on par with profitability. Some would say it takes precedence. For example, the industry’s dual focus on pro- ducing zero-emissions fuels while controlling emissions from major refinery conversion units, such as the fluid cat- alytic cracking (FCC) unit, demonstrates how sustainability can be achieved over a wider operating window. Against this backdrop, demonstrated sustainability can also be seen with more effective and environmen- tally benign catalysts, such as FCC additives with more durable precious metals via support surface morphology. Sustainability strategies play an important role in the elimination of hazardous byproducts ranging from metals contaminants to sulphur-bearing compounds. This calls for continuous addition to a catalyst’s capabilities, such as when upgrading biomass-derived materials. Much has been discussed on hydrocarbon feedstock pretreatment, such as FCC feed pretreatment. However, catalyst contamination and deactivation with the higher volumes of renewable and biofeeds entering the market are relatively new. For example, with the bioconversion of lignocellulosic feeds, conversion limits with these new feed types can be resolved using pretreatment systems to dis- integrate cross-linked fractions of lignocellulosic biomass. Pretreatment can avoid other unexpected challenges when introducing biomass feeds into a hydrotreater and its cata- lyst. For example, even when co-processing less than 10% biomass through a hydrotreater, problems such as dispro- portionately large heat releases have been observed.
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