Catalysis 2024 Issue

the 100+ wppm level, it will still require as much as twice the catalyst usage rate for 10% co-processing. A stable zeolite system and increased number of acid sites are key when processing these oils. Pore plugging metals, such as iron and calcium, are frequently observed at 1-10 wppm level in FCC feed. As the pores plug, the acces- sibility of the oils to the catalyst acid sites is reduced. This reduction in KAI will result in lower conversion and reduced transportation fuels. With these alternative feedstocks, unconventional con- taminant metals such as magnesium, phosphorous, zinc, silica, and manganese have been observed. These same metals frequently occur in FCC catalysts and additives themselves, but (in those cases) they do not exert the del- eterious influence associated with their presence as con - taminants. Magnesium has been seen as low as zero for refined, bleached, and deodorised (RBD) FOGs and as high as 150+ wppm in pyrolysis oils and crude FOGs. The phosphorous in co-processing feeds can reach levels up to 1000+ wppm, depending on the oil type and process- ing level, potentially accelerating or enhancing the effects of other contaminants such as iron. Silica in the feed will deposit on the catalyst’s surface along with other feed iron and calcium (or other alkali). This direct interaction of feed silica with iron and alkali results in enhanced pore plugging. The pore plugging metals may reach as high as 500 wppm depending on the refinement or demetalisation. FCC catalyst systems with high KAI and increased mesoporosity are key factors for processing this high pore plugging metal feed. Alternative deactivation protocols To develop catalyst technologies that can address the challenges associated with these metals, one must first understand and simulate the impact of these metals on catalyst properties and performance. Conventional labora- tory-scale FCC catalyst deactivation protocols do not rep- licate the impact of alternative metals and the formation of pore-plugging eutectics. To address this, Ketjen has developed alternative deac- tivation protocols to specifically replicate the catalyst pore plugging and surface densification associated with these contaminants in commercial operation. This protocol ena- bled the development of the next generation of metal-tol- erant catalysts, ReNewFCC-SG, specifically developed to maintain high accessibility and prevent pore plugging in the presence of new and higher metal contaminants. Utilising this new protocol to mimic the impact of Ni, V, Na, Si, Ca, P, and Fe on catalyst pore plugging and performance, a comparative evaluation was made between conventional catalyst and a new catalyst technology (ReNewFCC-SG) designed to resist the impact of these metals on catalyst surface porosity (lab-scale performance testing was done with a standard resid feed). At the same metal loading, the conventional catalyst exhibited only 38% of the initial acces- sibility (as indicated by KAI) after deactivation, whereas ReNewFCC-SG retained 92% of its fresh accessibility. The improved metals tolerance and accessibility main- tenance of ReNewFCC-SG compared to the conven - tional catalyst technology reflects the enhanced matrix

accessibility and stability of the former. The matrix technol- ogy of ReNewFCC results in a catalyst system whose per - formance is characterised by lower coke and slurry yields with improvement in gasoline and LPG olefin yields during co-processing of a PP-WPO (see Figure 4 ). Going forward Part II of this article will appear in PTQ Q2 2024 and pro - vide more clarity on how the engineering of catalysts with enhanced matrix accessibility, metals tolerance, corrosion resistance, and high accessibility allows FCC units to valorise more types of feeds. For example, refiners will see how other types of WPOs and feeds with elevated O2 and H 2 deficits can be converted to circular and renewable fuels and petro- chemical feedstocks. Against a backdrop of the challenges faced by refiners in co-processing biogenic, renewable, and recyclable feedstock, adding ReNewFCC to a refiner’s oper - ational strategy provides clear pathways to valorisation of FOGs, bio-oils, and WPOs.

ReNewFCC is a trademark of Ketjen Corporation.

References 1 www.iscc-system.org 2 IEA, www.iea.org/data-and-statistics/charts total-biofuel-production -by-feedstock-main-case-2021-2027 3 Avery C, Strohm J, FCC pathways to co-processing, Ketjen teaching module on co-processing 2023, PTQ Q4 2021. 4 Pinho A R, Almeida M B, Mendes F L, Ximenes V L, Casavechia L C, Co-processing raw bio-oil and gasoil in an FCC unit, Fuel Processing Technology, 131, 159-166, 2015. 5 Pinho A R, de Almeida M B, Mendes F L, Casavechia L C, Talmadge M S, Kinchin C M, Chum H L, Fast pyrolysis liquid co-processing from pinewood chips with vacuum gas oil in an FCC unit for second gener- ation fuel production, Fuel , 188, 462-473, 2017. 6 Petrobras processes 100% renewable feed in Riograndense FCC, OGJ Newsletter, Dec. 4, 2023, www.ogj.com/refining-processing/ petrochemicals/article/14301266/petrobras-processes-100-renewable -feed-in-riograndense-fcc 7 Claesen C, Nalco water solutions when producing biofuels, pre - sented at 2023 Ketjen FCC workshop, Hanoi. Jon Strohm is a R&D Advisor within Ketjen’s FCC R&D in Pasadena, Texas. He leads R&D efforts in the development of new catalytic mate - rials for current and emerging FCC technologies. He has more than 25 years of experience in thermochemical and catalytic hydrocarbon conversions. Darrell Rainer is the Global FCC VGO Specialist with Ketjen Corporation, Houston, Texas. In this role, he works with R&D and busi - ness groups to develop and market new catalyst technologies. He has an R&D background, and more than 27 years of experience in FCC, hydroprocessing, and biofuels. Oscar Oyola-Rivera is an R&D Chemist at Ketjen’s FCC R&D and Project Manager for ReNewFCC. He also leads R&D efforts to develop new catalytic materials for current and future emerging FCC catalysts. He has more than 10 years of experience in heterogeneous catalytic processes for the conversion of hydrocarbons, biomass, and CO2 . Clifford Avery is Global FCC Process Advisor with Ketjen Corporation, Houston, Texas. In this role he leads the global FCC effort in training, troubleshooting, and performing unit health checks. Avery has more than 38 years of experience with FCC and other refining processes.

Catalysis 2024