Selectivity Control and Catalyst Design in the Fischer-Tropsch Synthesis: Sites, Pellets, and Reactors

Iglesia, Enrique; Reyes, Sebastián C.; Madon, R.J.; Soled, S.

doi:10.1016/s0360-0564(08)60579-9

Cited by 404 publications

(333 citation statements)

References 104 publications

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“…A possible explanation is that with the use of nanometric and non-porous materials, no diffusion limitations existed and hence the apparent instantaneously availability of the FTS products in the solvent for analysis. Besides, it is also thought that since the heavier hydrocarbons take longer to move away from the catalyst surface, by virtue of their size, they have greater re-adsorption probability after formation [51]. Other authors indeed agree with the supposition that the olefin-chain length influences re-adsorption rate because the strength of molecular physisorption on catalyst surface increases its solubility in FTS wax with growing chain length and this olefin re-adsorption model was used to accurately predict product selectivity over the entire range of their experimental conditions [14].…”

Section: Catalyst Selectivity and α-Valuesmentioning

confidence: 99%

Effect of CO Concentration on the α-Value of Plasma-Synthesized Co/C Catalyst in Fischer-Tropsch Synthesis

Aluha

Abatzoglou

2017

Catalysts

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Abstract:A plasma-synthesized cobalt catalyst supported on carbon (Co/C) was tested for Fischer-Tropsch synthesis (FTS) in a 3-phase continuously-stirred tank slurry reactor (3-φ-CSTSR) operated isothermally at 220 • C (493 K), and 2 MPa pressure. Initial syngas feed stream of H 2 :CO ratio = 2 with molar composition of 0.6 L/L (60 vol %) H 2 and 0.3 L/L (30 vol %) CO, balanced in 0.1 L/L (10 vol %) Ar was used, flowing at hourly space velocity (GHSV) of 3600 cm 3 ·h −1 ·g −1 of catalyst. Similarly, other syngas feed compositions of H 2 :CO ratio = 1.5 and 1.0 were used. Results showed~40% CO conversion with early catalyst selectivity inclined towards formation of gasoline (C 4 -C 12 ) and diesel (C 13 -C 20 ) fractions. With prolonged time-on-stream (TOS), catalyst selectivity escalated towards the heavier molecular-weight fractions such as waxes (C 21+ ). The catalyst's α-value, which signifies the probability of the hydrocarbon-chain growth was empirically determined to be in the range of 0.85-0.87 (at H 2 :CO ratio = 2), demonstrating prevalence of the hydrocarbon-chain propagation, with particular predisposition for wax production. The inhibiting CO effect towards FTS was noted at molar H 2 :CO ratio of 1.0 and 1.5, giving only~10% and~20% CO conversion respectively, although with a high α-value of 0.93 in both cases, which showed predominant production of the heavier molecular weight fractions.

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Section: Catalyst Selectivity and α-Valuesmentioning

confidence: 99%

Effect of CO Concentration on the α-Value of Plasma-Synthesized Co/C Catalyst in Fischer-Tropsch Synthesis

Aluha

Abatzoglou

2017

Catalysts

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“…Futhermore, it is unlikely that olefin reincorporation is due to longer residence time in pores, as is the fundamental explanation behind the diffusion-controlled model of Iglesia et al [44].…”

Section: Chemical Reactions and Kineticsmentioning

confidence: 98%

A Fischer-Tropsch synthesis reactor model framework for liquid biofuels production.

Pratt¹

2012

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Fischer-Tropsch synthesis (FTS) is an attractive option in the process of converting biomass-derived syngas to liquid fuels in a small-scale mobile bio-refinery. Computer simulation can be an efficient method of designing a compact FTS reactor, but no known comprehensive model exists that is able to predict performance of the needed non-traditional designs.This work developed a generalized model framework that can be used to examine a variety of FTS reactor configurations. It is based on the four fundamental physics areas that underlie FTS reactors: momentum transport, mass transport, energy transport, and chemical kinetics, rather than empirical data of traditional reactors.The mathematics developed were applied to an example application and solved numerically using COMSOL. The results compare well to the literature and give insights into the operation of FTS that are then used to propose a new reactor concept that may be suitable for the mobile bio-refinery application. 4 AcknowledgementsI am deeply grateful to the Sandia LDRD office and the ECIS investment area for sponsoring this project.I would also like to thank the following people who participated in this project:• Chris Shaddix for his mentorship, both technically and personally, throughout the project.• Hank Westrich and Sheri Martinez at the LDRD Office for their assistance and encouragement.• Daniel Dedrick for his work in forming the concept of this LDRD topic.• Blake Simmons for providing project management so I could focus on the technical challenges.• Deanna Agosta for financial planning.• Tiffany Vargas and Karen McWilliams at the CA Technical Library for providing and/or helping me find the countless papers and texts used to develop my understanding of everything from the detailed theory to the history and applications of FTS. 5 SummaryLiquid fuels synthesized from renewable CO and H 2 could displace petroleum-based fuels to provide clean, renewable energy for the future. Small scale (<20 bbl/day) reactors for synthetic liquid fuels production are an emerging development area that may enable mobile biomass-to-liquids plants suited for on-demand liquid fuel production from diverse, underutilized, local resources. The design of such a "mobile bio-refinery" is a significant departure from the traditional large-scale industrial designs and requires predictive tools such as computer models to efficiently produce a successful facility. Because existing models inherently incorporate the empirical results of the traditional designs they are not suitable for this application. The need for a model that can examine the drastic design changes and innovations needed for the mobile bio-refinery is clear.The goal of this work was to create a gas-to-liquids synthesis model with the minimum amount of empiricism and assumptions allowed by the current state of the theory, through integrated physics component models across varying length scales, with the ultimate purpose being to enable design of efficient, durable, and flexible small scale and/or novel re...

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“…If diffusion limitations become significant, hydrogen diffusion in pores will be faster than CO diffusion. This could lead to CO-deficient areas in catalyst particles, with methanation, lower weight hydrocarbon products and higher paraffin/olefin ratio as the consequence 39,40 .…”

Section: Cobalt Catalystsmentioning

confidence: 99%

Fischer‒Tropsch Conversion of Biomass‐Derived Synthesis Gas to Liquid Fuels

Lillebø¹,

Holmén²,

Enger³

et al. 2015

Advances in Bioenergy

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Selectivity Control and Catalyst Design in the Fischer-Tropsch Synthesis: Sites, Pellets, and Reactors

Cited by 404 publications

References 104 publications

Effect of CO Concentration on the α-Value of Plasma-Synthesized Co/C Catalyst in Fischer-Tropsch Synthesis

Effect of CO Concentration on the α-Value of Plasma-Synthesized Co/C Catalyst in Fischer-Tropsch Synthesis

A Fischer-Tropsch synthesis reactor model framework for liquid biofuels production.

Fischer‒Tropsch Conversion of Biomass‐Derived Synthesis Gas to Liquid Fuels

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