Evaluation of alumina-supported Mo carbide produced via propane carburization for the Fischer-Tropsch synthesis

Dai Viet N Vo, Cyrus G. Cooper, Tuan Huy Nguyen, Adesoji A. Adesina, Dragomir B. Bukur

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

CO hydrogenation over alumina-supported Mo carbide catalyst synthesized by temperature-programmed carburization of the impregnated MoO 3 utilizing H 2/C 3H 8 feed has been investigated. Samples were prepared following a 2 3-factorial design with temperature, hydrocarbon composition and reaction time as the carburization factors. Catalysts were characterized using N 2 physisorption, NH 3 temperature-programmed desorption and solid total organic carbon (TOC) analysis. Solid-state carburization kinetics was studied in a thermogravimetric analyzer at different heating rates. Statistical analysis revealed that carburization temperature was a strong determinant of key physicochemical properties (BET, pore volume, acid site strength and concentration). Increasing the H 2:C 3H 8 ratio in the carburizing gas reduced the acid site strength and concentration but improved overall hydrocarbon synthesis rate, olefin-to-paraffin ratio and specific activity. All catalysts possessed Lewis acid centers. The carburizing temperature was also a statistically significant factor in the determination of the FT reaction metrics. A two-stage process involving the transformation of Mo oxide to the MoC 1-x carbide via an intermediate oxycarbide phase was observed. The solid-state kinetics was captured by a contracting volume model and Arrhenius treatment implicated the occurrence of a 'compensation effect' for the carbothermal synthesis. Although the rate-composition envelope exhibited qualitatively similar features for the entire Mo carbide class, the optimum feed composition for maximum hydrocarbon formation rate varied between 0.67 and 0.75 depending on the catalyst preparation conditions and the carbon number. The olefin-to-paraffin ratio has a reciprocal relationship to the H 2 partial pressure but experienced an exponential decay with carbon number. Catalyst with 15 wt.% Mo loading produced the highest hydrocarbon synthesis rate and chain growth probability.

Original languageEnglish
Pages (from-to)105-116
Number of pages12
JournalFuel
Volume93
DOIs
Publication statusPublished - Mar 2012

Fingerprint

Propane
Fischer-Tropsch synthesis
Aluminum Oxide
Carbides
Hydrocarbons
Alumina
Catalysts
Carburizing
Alkenes
Paraffin
Paraffins
Olefins
Acids
Carbon
Chemical analysis
Lewis Acids
Temperature
Kinetics
Physisorption
Carbon Monoxide

Keywords

  • Compensation effect in heterogeneous catalytic kinetics
  • Factorial design
  • Fischer-Tropsch synthesis
  • Molybdenum carbide
  • Regression polynomials

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Fuel Technology
  • Energy Engineering and Power Technology
  • Organic Chemistry

Cite this

Evaluation of alumina-supported Mo carbide produced via propane carburization for the Fischer-Tropsch synthesis. / Vo, Dai Viet N; Cooper, Cyrus G.; Nguyen, Tuan Huy; Adesina, Adesoji A.; Bukur, Dragomir B.

In: Fuel, Vol. 93, 03.2012, p. 105-116.

Research output: Contribution to journalArticle

Vo, Dai Viet N ; Cooper, Cyrus G. ; Nguyen, Tuan Huy ; Adesina, Adesoji A. ; Bukur, Dragomir B. / Evaluation of alumina-supported Mo carbide produced via propane carburization for the Fischer-Tropsch synthesis. In: Fuel. 2012 ; Vol. 93. pp. 105-116.
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abstract = "CO hydrogenation over alumina-supported Mo carbide catalyst synthesized by temperature-programmed carburization of the impregnated MoO 3 utilizing H 2/C 3H 8 feed has been investigated. Samples were prepared following a 2 3-factorial design with temperature, hydrocarbon composition and reaction time as the carburization factors. Catalysts were characterized using N 2 physisorption, NH 3 temperature-programmed desorption and solid total organic carbon (TOC) analysis. Solid-state carburization kinetics was studied in a thermogravimetric analyzer at different heating rates. Statistical analysis revealed that carburization temperature was a strong determinant of key physicochemical properties (BET, pore volume, acid site strength and concentration). Increasing the H 2:C 3H 8 ratio in the carburizing gas reduced the acid site strength and concentration but improved overall hydrocarbon synthesis rate, olefin-to-paraffin ratio and specific activity. All catalysts possessed Lewis acid centers. The carburizing temperature was also a statistically significant factor in the determination of the FT reaction metrics. A two-stage process involving the transformation of Mo oxide to the MoC 1-x carbide via an intermediate oxycarbide phase was observed. The solid-state kinetics was captured by a contracting volume model and Arrhenius treatment implicated the occurrence of a 'compensation effect' for the carbothermal synthesis. Although the rate-composition envelope exhibited qualitatively similar features for the entire Mo carbide class, the optimum feed composition for maximum hydrocarbon formation rate varied between 0.67 and 0.75 depending on the catalyst preparation conditions and the carbon number. The olefin-to-paraffin ratio has a reciprocal relationship to the H 2 partial pressure but experienced an exponential decay with carbon number. Catalyst with 15 wt.{\%} Mo loading produced the highest hydrocarbon synthesis rate and chain growth probability.",
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AU - Bukur, Dragomir B.

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AB - CO hydrogenation over alumina-supported Mo carbide catalyst synthesized by temperature-programmed carburization of the impregnated MoO 3 utilizing H 2/C 3H 8 feed has been investigated. Samples were prepared following a 2 3-factorial design with temperature, hydrocarbon composition and reaction time as the carburization factors. Catalysts were characterized using N 2 physisorption, NH 3 temperature-programmed desorption and solid total organic carbon (TOC) analysis. Solid-state carburization kinetics was studied in a thermogravimetric analyzer at different heating rates. Statistical analysis revealed that carburization temperature was a strong determinant of key physicochemical properties (BET, pore volume, acid site strength and concentration). Increasing the H 2:C 3H 8 ratio in the carburizing gas reduced the acid site strength and concentration but improved overall hydrocarbon synthesis rate, olefin-to-paraffin ratio and specific activity. All catalysts possessed Lewis acid centers. The carburizing temperature was also a statistically significant factor in the determination of the FT reaction metrics. A two-stage process involving the transformation of Mo oxide to the MoC 1-x carbide via an intermediate oxycarbide phase was observed. The solid-state kinetics was captured by a contracting volume model and Arrhenius treatment implicated the occurrence of a 'compensation effect' for the carbothermal synthesis. Although the rate-composition envelope exhibited qualitatively similar features for the entire Mo carbide class, the optimum feed composition for maximum hydrocarbon formation rate varied between 0.67 and 0.75 depending on the catalyst preparation conditions and the carbon number. The olefin-to-paraffin ratio has a reciprocal relationship to the H 2 partial pressure but experienced an exponential decay with carbon number. Catalyst with 15 wt.% Mo loading produced the highest hydrocarbon synthesis rate and chain growth probability.

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KW - Molybdenum carbide

KW - Regression polynomials

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