Advanced fundamental modeling of the kinetics of Fischer–Tropsch synthesis

Zhou, Liping; Froment, Gilbert F.; Yang, Yong; Li, Yongwang

doi:10.1002/aic.15141

Cited by 15 publications

(15 citation statements)

References 41 publications

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“…Two recent microkinetic studies utilized the single‐event kinetic approach in developing detailed models for Co catalysts . Both report that methane formation can be explained by taking into account higher symmetry numbers of methane, a feature specific for the single‐event microkinetic approach.…”

Section: Resultsmentioning

confidence: 99%

“…This issue is highly relevant from an industrial standpoint because methane presents the most undesired product of FTS. In previous detailed kinetic models, it was assumed that the rate constant for methane formation is different from rate constants for C 2+ n ‐paraffin products . However, there are strong indications that the reasons for methane deviations are more complex and could be related to the possible existence of different reaction pathways .…”

Section: Introductionmentioning

confidence: 99%

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Kinetic Modeling of Secondary Methane Formation and 1‐Olefin Hydrogenation in Fischer–Tropsch Synthesis over a Cobalt Catalyst

Todić

Ma²,

Jacobs

et al. 2017

Int J of Chemical Kinetics

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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-thanexpected 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 Correspondence to: Branislav Todic; e-mail: branislav.todic@ qatar.tamu.edu.Supporting Information is available in the online issue at www.wileyonlinelibrary.com. C 2017 Wiley Periodicals, Inc. 860TODIC ET AL.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.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Kinetic Modeling of Secondary Methane Formation and 1‐Olefin Hydrogenation in Fischer–Tropsch Synthesis over a Cobalt Catalyst

Todić

Ma²,

Jacobs

et al. 2017

Int J of Chemical Kinetics

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“…We coded the kinetics of the FT reaction in Python 3.9.4. We employed a model that considers an iron catalyst and calculates the paraffin, olefin and alcohol distributions based on 7 micro-kinetics rate steps [41]. The model also considers the water-gas shift reaction (see Supporting Information).…”

Section: Process Simulationmentioning

confidence: 99%

Gas to Liquids Techno-Economics of Associated Natural Gas, Bio Gas, and Landfill Gas

et al. 2021

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Methane is the second highest contributor to the greenhouse effect. Its global warming potential is 37 times that of CO2. Flaring-associated natural gas from remote oil reservoirs is currently the only economical alternative. Gas-to-liquid (GtL) technologies first convert natural gas into syngas, then it into liquids such as methanol, Fischer–Tropsch fuels or dimethyl ether. However, studies on the influence of feedstock composition are sparse, which also poses technical design challenges. Here, we examine the techno-economic analysis of a micro-refinery unit (MRU) that partially oxidizes methane-rich feedstocks and polymerizes the syngas formed via Fischer–Tropsch reaction. We consider three methane-containing waste gases: natural gas, biogas, and landfill gas. The FT fuel selling price is critical for the economy of the unit. A Monte Carlo simulation assesses the influence of the composition on the final product quantity as well as on the capital and operative expenses. The Aspen Plus simulation and Python calculate the net present value and payback time of the MRU for different price scenarios. The CO2 content in biogas and landfill gas limit the CO/H2 ratio to 1.3 and 0.9, respectively, which increases the olefins content of the final product. Compressors are the main source of capital cost while the labor cost represents 20–25% of the variable cost. An analysis of the impact of the plant dimension demonstrated that the higher number represents a favorable business model for this unit. A minimal production of 7,300,000 kg y−1 is required for MRU to have a positive net present value after 10 years when natural gas is the feedstock.

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“…21,22 Numerous studies have been recently devoted to Fischer-Tropsch kinetics, and accurate models are now available in the literature. [23][24][25][26][27][28][29] Some of them take the deactivation phenomena into account in the proposed model, which is necessary to predict long-term performances. Visconti et al 30 for instance introduced a dependency of the CO consumption rate to the sulfur content of the syngas, to represent the deactivation linked to sulfur poisoning.…”

Section: Introductionmentioning

confidence: 99%

Impact of cobalt catalyst carburization on Fischer‐Tropsch micro‐kinetics

et al. 2022

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Recent models of the Fischer‐Tropsch synthesis are able to predict quite accurately the catalyst's initial activity and selectivity. However, these micro‐kinetic models rarely consider the performance loss with time on stream and in particular the heavy product selectivity loss. In this study, a deactivation model at the micro‐kinetic scale is proposed to represent the effect of carburization on Fischer‐Tropsch catalysts performances. Comparison of different mechanisms revealed that termination reactions were the most affected by cobalt carbide formation, before reactants adsorption or chain growth. Both activity and selectivity decline could be accurately described using linear and second‐order power laws expressions of active sites concentration and termination kinetic rate constants. The obtained model predicts a monotonous evolution of activity and selectivities from 10% to 80% carburization, above which an important increase of olefin selectivity is observed. The model did not indicate any change of the surface coverages after carburization.

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Advanced fundamental modeling of the kinetics of Fischer–Tropsch synthesis

Cited by 15 publications

References 41 publications

Kinetic Modeling of Secondary Methane Formation and 1‐Olefin Hydrogenation in Fischer–Tropsch Synthesis over a Cobalt Catalyst

Kinetic Modeling of Secondary Methane Formation and 1‐Olefin Hydrogenation in Fischer–Tropsch Synthesis over a Cobalt Catalyst

Gas to Liquids Techno-Economics of Associated Natural Gas, Bio Gas, and Landfill Gas

Impact of cobalt catalyst carburization on Fischer‐Tropsch micro‐kinetics

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