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dc.contributor.authorJeske, Kai-
dc.contributor.authorKızılkaya, Ali Can-
dc.contributor.authorLopez-Luque, Ivan-
dc.contributor.authorPfaender, Norbert-
dc.contributor.authorBartsch, Mathias-
dc.contributor.authorConcepcion, Patricia-
dc.contributor.authorPrieto, Gonzalo-
dc.description.abstractAdjusting hydrocarbon product distributions in the Fischer-Tropsch (FT) synthesis is of notable significance in the context of so-called X-to-liquids (XTL) technologies. While cobalt catalysts are selective to long-chain paraffin precursors for synthetic jet- and diesel-fuels, lighter (C10-) alkane condensates are less valuable for fuel production. Alternatively, iron carbide-based catalysts are suitable for the coproduction of paraffinic waxes alongside liquid (and gaseous) olefin chemicals; however, their activity for the water-gas-shift reaction (WGSR) is notoriously detrimental when hydrogen-rich syngas feeds, for example, derived from (unconventional) natural gas, are to be converted. Herein the roles of pore architecture and oxide promoters of Lewis basic character on CoRu/Al2O3 FT catalysts are systematically addressed, targeting the development of catalysts with unusually high selectivity to liquid olefins. Both alkali and lanthanide oxides lead to a decrease in turnover frequency. The latter, particularly PrOx, prove effective to boost the selectivity to liquid (C5-10) olefins without undesired WGSR activity. In situ CO-FTIR spectroscopy suggests a dual promotion via both electronic modification of surface Co sites and the inhibition of Lewis acidity on the support, which has direct implications for double-bond isomerization reactivity and thus the regioisomery of liquid olefin products. Density functional theory calculations ascribe oxide promotion to an enhanced competitive adsorption of molecular CO versus hydrogen and olefins on oxide-decorated cobalt surfaces, dampening (secondary) olefin hydrogenation, and suggest an exacerbated metal surface carbophilicity to underlie the undesired induction of WGSR activity by strongly electron-donating alkali oxide promoters. Enhanced pore molecular transport within a multimodal meso-macroporous architecture in combination with PrOx as promoter, at an optimal surface loading of 1 Prat nm(-2), results in an unconventional product distribution, reconciling benefits intrinsic to Co- and Fe-based FT catalysts, respectively. A chain-growth probability of 0.75, and thus >70 C% selectivity to C5+ products, is achieved alongside lighter hydrocarbon (C5-10) condensates that are significantly enriched in added-value chemicals (67 C%), predominantly alpha-olefins but also linear alcohols, remarkably with essentially no CO2 side-production (<1%). Such unusual product distributions, integrating precursors for synthetic fuels and liquid platform chemicals, might be desired to diversify the scope and improve the economics of small-scale gas- and biomass-to-liquid processes.en_US
dc.description.sponsorshipEuropean Union's Horizon 2020 research and innovation programme [817612]; Max Planck SocietyMax Planck SocietyFoundation CELLEX; Bundesministerium fur Bildung und ForschungFederal Ministry of Education & Research (BMBF) [01DG17019]; Spanish Ministry of Science and Innovation (`Severo Ochoa Excellence Program') [SEV-2016-0683]; European Research CouncilEuropean Research Council (ERC)European Commission [ERC-2019-CoG-864195]en_US
dc.description.sponsorshipSasol Materials is very gratefully acknowledged for the supply of high-purity pseudoboehmite alumina precursors. M. G. Farpon (ITQ) is acknowledged for 2-butene olefin isomer equilibrium composition determinations with Aspen Plus (AspenTech). J.M. Salas (ITQ) is acknowledged for his contributions to the CO-FTIR studies. A. Mun~oz and M.D. Soriano (ITQ) are acknowledged for the XPS experiments, and M. Arribas (ITQ) for H2-chemisorption measurements. M. Meyer and V. Dietl (MPI-KOFO) and V. Recio (ITQ) are acknowledged for technical assistance with lab work and offline GC product analyses. Prof. A. Lorke (UDE) is gratefully acknowledged for access to dual-beam facilities. We thank Prof. F. Schu<spacing diaeresis>th (MPI-KOFO) for the allocation of lab space and supportive access to research instrumentation. This project has received funding from the European Union's Horizon 2020 research and innovation programme under Grant Agreement no. 817612 (REDIFUEL). Additionally, parts of this research received funding by the Max Planck Society, the Bundesministerium fur Bildung und Forschung (grant number 01DG17019), the Spanish Ministry of Science and Innovation (`Severo Ochoa Excellence Program' (SEV-2016-0683)) and the European Research Council (grant ERC-2019-CoG-864195). DFT calculations were performed at the EFES computing cluster located in the Izmir Institute of Technology (IZTECH). A.C.K. thanks IZTECH for the allocation of computational time.en_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.ispartofACS Catalysisen_US
dc.subjectHierarchical porosityen_US
dc.subjectPromotion effectsen_US
dc.subjectLinear olefinsen_US
dc.subjectDFT calculationsen_US
dc.titleDesign of cobalt Fischer-Tropsch catalysts for the combined production of liquid fuels and olefin chemicals from hydrogen-rich syngasen_US
dc.institutionauthorKızılkaya, Ali Can-
dc.departmentİzmir Institute of Technology. Chemical Engineeringen_US
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanıen_US
dc.authorwosidKizilkaya, Ali Can/AAK-9132-2020-
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item.cerifentitytypePublications- Department of Chemical Engineering-
Appears in Collections:Chemical Engineering / Kimya Mühendisliği
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