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Kinetic Modeling of Secondary Methane Formation and 1‐Olefin Hydrogenation in Fischer–Tropsch Synthesis over a Cobalt Catalyst
Author(s) -
Todic Branislav,
Ma Wenping,
Jacobs Gary,
Nikacevic Nikola,
Davis Burtron H.,
Bukur Dragomir B.
Publication year - 2017
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.21133
Subject(s) - olefin fiber , fischer–tropsch process , chemistry , methane , catalysis , cobalt , slurry , inorganic chemistry , organic chemistry , thermodynamics , selectivity , physics
A detailed kinetic model of Fischer–Tropsch synthesis (FTS) product formation, including secondary methane formation and 1‐olefin hydrogenation, has been developed. Methane formation in FTS over the cobalt‐based catalyst is well known to be higher‐than‐expected compared to other n ‐paraffin products under typical reaction conditions. A novel model proposes secondary methane formation on a different type of active site, which is not active in forming C 2+ products, to explain this anomalous methane behavior. In addition, a model of secondary 1‐olefin hydrogenation has also been developed. Secondary 1‐olefin hydrogenation is related to secondary methane formation with both reactions happening on the same type of active sites. The model parameters were estimated from experimental data obtained with Co/Re/γ‐Al 2 O 3 catalyst in a slurry‐phase stirred tank reactor over a range of conditions ( T = 478, 493, and 503 K, P = 1.5 and 2.5 MPa, H 2 /CO feed ratio = 1.4 and 2.1, and X CO = 16–62%). The proposed model including secondary methane formation and 1‐olefin hydrogenation is shown to provide an improved quantitative and qualitative prediction of experimentally observed behavior compared to the detailed model with only primary reactions.