PTQ Q1 2024 Issue

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,

PTQ Q1 2024