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Comparative Simulations of Cobalt- and Iron-Based Fischer-Tropsch Synthesis Slurry Bubble Column Reactors

Ion Iliuta, Faı̈çal Larachi, Jérôme Anfray, Nicolas Dromard, D. Schweich

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Abstract

The influence of the catalyst type (Fe and Co) on CO and H 2 conversions, CO 2 selectivity, and the composition in Fischer-Tropsch synthesis slurry bubble column reactors was simulated for representative commercial-scale units (7 m i.d. and 30 m height). A nonisothermal, core-annulus multicompartment multicomponent two-bubble class model was used to account for a relatively detailed hydrodynamics. It was coupled to comprehensive Fischer-Tropsch synthesis and water−gas-shift reactions, in addition to descriptions of thermodynamics and thermal effects, variable gas flow rate due to chemical/physical contraction, and gas and slurry backmixing and (re)circulation. Two mechanistic kinetic models with consideration of olefin readsorption were employed to describe the paraffin and olefin formation with cobalt- and iron-based catalysts, in addition to relatively large activities for CO 2 and oxygenate formation, mainly alcohols, for the latter catalyst. The influence of the temperature and superficial gas velocity on CO and H 2 conversions was more evident for a cobalt-based catalyst. For both catalysts, the space-dependent superficial gas velocity directly affected the gas-phase mean residence time, influencing in the return reactor temperature and conversions. Reliable estimation of the gas velocity due to chemical contraction was critical for conversions exceeding 50%. For both catalysts, the nonisothermal simulations reveal that, because heat removal is well managed from the heat-exchange area, the reactor operation can be considered as nearly isothermal.

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What this paper is about

The influence of the catalyst type (Fe and Co) on CO and H 2 conversions, CO 2 selectivity, and the composition in Fischer-Tropsch synthesis slurry bubble column reactors was simulated for representative commercial-scale units (7 m i.d. and 30 m height). A nonisothermal, core-annulus multicompartment multicomponent two-bubble class model was used to account for a relatively detailed hydrodynamics. It was coupled to comprehensive Fischer-Tropsch synthesis and water−gas-shift reactions, in addition to descriptions of thermodynamics and thermal effects, variable gas flow rate due to chemical/physical contraction, and gas and slurry backmixing and (re)circulation. Two mechanistic kinetic models with consideration of olefin readsorption were employed to describe the paraffin and olefin formation with cobalt- and iron-based catalysts, in addition to relatively large activities for CO 2 and oxygenate formation, mainly alcohols, for the latter catalyst. The influence of the temperature and superficial gas velocity on CO and H 2 conversions was more evident for a cobalt-based catalyst. For both catalysts, the space-dependent superficial gas velocity directly affected the gas-phase mean residence time, influencing in the return reactor temperature and conversions. Reliable estimation of the gas velocity due to chemical contraction was critical for conversions exceeding 50%. For both catalysts, the nonisothermal simulations reveal that, because heat removal is well managed from the heat-exchange area, the reactor operation can be considered as nearly isothermal.

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Available abstract

The influence of the catalyst type (Fe and Co) on CO and H 2 conversions, CO 2 selectivity, and the composition in Fischer-Tropsch synthesis slurry bubble column reactors was simulated for representative commercial-scale units (7 m i.d. and 30 m height). A nonisothermal, core-annulus multicompartment multicomponent two-bubble class model was used to account for a relatively detailed hydrodynamics. It was coupled to comprehensive Fischer-Tropsch synthesis and water−gas-shift reactions, in addition to descriptions of thermodynamics and thermal effects, variable gas flow rate due to chemical/physical contraction, and gas and slurry backmixing and (re)circulation. Two mechanistic kinetic models with consideration of olefin readsorption were employed to describe the paraffin and olefin formation with cobalt- and iron-based catalysts, in addition to relatively large activities for CO 2 and oxygenate formation, mainly alcohols, for the latter catalyst. The influence of the temperature and superficial gas velocity on CO and H 2 conversions was more evident for a cobalt-based catalyst. For both catalysts, the space-dependent superficial gas velocity directly affected the gas-phase mean residence time, influencing in the return reactor temperature and conversions. Reliable estimation of the gas velocity due to chemical contraction was critical for conversions exceeding 50%. For both catalysts, the nonisothermal simulations reveal that, because heat removal is well managed from the heat-exchange area, the reactor operation can be considered as nearly isothermal.

Key concepts: Fischer–Tropsch process, Cobalt, Catalysis, Chemistry, Slurry, Bubble column reactor, Water gas, Isothermal process

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