PTQ Q3 2022 Issue

improved attrition resistance and hydrothermal stabil- ity., In addition to P, incorporation of Fe₂O₃ and/or B₂O₃ leads to higher isobutene and LPG yields and lower coke production. In the coming decades, the energy and chemicals markets will face a very important reshaping. Chemicals represent one of the fastest-growing crude-oil-demand sectors. The use of oil in the petrochemicals sector is likely to become a key source of oil demand after the 2020s. At the same time, environmental regulations predicate the use of bio- feedstocks and waste (such as plastic waste) to deliver products for the petrochemical value chain (such as olefins and polymers). For this task, FCC units become a major pro- pylene source with minimal energy intensity. Consequences One of the consequences of this petrochemical shift in the way refineries operate in the future can be seen in the pro - cess and catalyst development challenges and the research opportunities therein. Against this backdrop, the refinery of the future, with CO₂ neutrality as a major objective, will achieve its objectives through breakthroughs in some of the following intertwined areas: • Maximisation of chemicals production with integrated carbon capture • CO₂ capture and transformation to products such as e-fuels, olefins, and other products for the chemical industry • Reduce emissions along with the use of renewable energy in the process • Process intensification by miniaturisation of physical foot - print where applicable and overall maximum reduction in the number of unit operations, thereby significantly reduc - ing energy and capital intensity •Integration of new intelligent process control systems for implementing rapidly corrective and preventive actions (in line with market demands) • Discovery of scalable multifunctional catalysts able to upgrade (i.e., removal of crude oil and biofeed impurities) and crack light olefins and aromatics in one single reaction vessel • New feeds, biofeeds, waste, plastic recycling, and differ- ent products coming from the circular economy. The goal is to characterise each significant fragment of the feed molecules, sort them by class, correlate them to yields and product quality, and improve catalyst and absorbents/ adsorbents • The success of the refinery of the future will rest on the development of economically efficient processes based on minimal steps while using renewable energies. The end-game is that refinery and petrochemical integra - tion will take on increased importance in the future, where process units can share equipment while producing more value-added products. High chemical yields The combination of new multifunctional catalysts, new reactor concepts, process intensification, and smart inte - gration of renewable energy and biofeeds should result in the development of new processes, surpassing an 80 wt%

FCC Commercial Process

Dierent operation modes

1942 Model I upow 1943 Model II downow 1945 Sinclair design 1947 Model II side by side 1951 Kellogg orthoow A 1952 Exxon model IV 1953 Kellogg orthoow B 1955 Shell two-stage reactor 1956 UOP straight riser 1958 Exxon riser cracker 1961 HOC cracker (Phillips) 1962 Kellogg orthoow C 1967 Texaco design 1971 Gulf FCC process 1972 Exxon exicracker 1972 Amoco ultracracking 1973 UOP high eciency design 1973 Kellogg orthoow F 1981 Total petroleum resid cracker 1982 Ashland/UOP RCC unit 1985 IFP R2R 1990 Kellogg/Mobil HOC 1991 Deep catalytic cracking (RIPP and S&W) 1993 Exxon exicracker III 1996 MSCC UOP/Coastal 2002 Catalytic pyrolysis process 2010 Doble Riser (KBR/Shell)

Hydrotreated and non- hydrotreated VGO Olens Gasoline Gasoline RON & MON Middle destilates VGO + residue feed

Process development

Particles diminished 2, 3, 4 cyclons steps Wtgas scrubber NOx additives and Regenerator Tem. Stripping equipment Feed nozzles (dispersion

improvement) Catalyst cooler

Double regenerator Methanol to gasoline Methanol to olens Aromatics production Bio feeds (in progress) Crude oil downow (in progress)

Figure 2 FCC process and catalyst innovations since 1940s

feedstocks has a substantial, positive impact on FCC unit conversion. Hydroprocessing of cracker feeds, vacuum gas oil (VGO) or mild hydrocracking/hydrocracking of VGO and residues has a dramatic effect on FCC unit performance, basically because hydroprocessing increases the ratio H/C in streams fed to the FCC. The resulting product makes a good feed for FCCs, reduc- ing catalyst make-up, obtaining a better-quality product with less sulphur, and increasing yields of valued products while diminishing SOx and NOx emissions. Selectivity In contrast to noncatalytic processes, the use of FCC allows for better control over product selectivity. Many FCC systems for processing VGO and/or oil residues to produce light olefins have been developed and commercialised. As summarised and reviewed by Bogle and Corma, most of these technologies rely on high-severity operations using single or dual riser reactors with optional naphtha recy- cling. Injection of recycled naphtha is preferred at the end of the riser or in a second riser to minimise dry gas and coke yields. Together with USY, ZSM-5 is the second most widely used zeolite in catalytic cracking applications. Initially added in smaller amounts as a gasoline booster, the use of ZSM-5 also increases propylene production by 1-5 wt% over con- ventional FCC processes that yield 4-6 wt% of propylene. Oil-to-chemicals technologies are expected to increase this number up to 20 wt%. A key aspect of improving light olefin yield (in addition to higher temperatures) is the modification of the parent zeolite to minimise hydrogen transfer reactions (and conse- quently aromatisation and coke formation). Phosphorus stabilisation has been shown to result not only in lower hydrogen transfer ability but also in

PTQ Q3 2022