Mixed alcohol synthesis from carbon monoxide and dihydrogen over potassium-promoted molybdenum carbide catalysts

Woo, Hee Chul; Park, Ki Yeop; Kim, Young Gul; ShikChung, In-Sik Namau]Jong; Lee, Jae Sung

doi:10.1016/s0166-9834(00)83136-x

Cited by 153 publications

(59 citation statements)

References 18 publications

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“…Generally it can be observed that the synthesis yields preferentially DME, low molecular weight hydrocarbons and linear alcohols with up to four carbon atoms. According to a review by Surisetty et al [6] the alcohol products over alkali-promoted molybdenum-based catalysts are linear alcohols and the mechanism for formation of higher alcohols is via a classical insertion of CO into the corresponding precursor alcohol [44]. The presence however of secondary alcohols in the product mix suggests that chain-growth also takes place via an aldol condensation pathway.…”

Section: Effect Of Type and Pre-treatment Of Activated Carbon Supportmentioning

confidence: 99%

K-promoted NiMo catalysts supported on activated carbon for the hydrogenation reaction of CO to higher alcohols: Effect of support and active metal

Liakakou

Heracleous

Triantafyllidis

et al. 2015

Applied Catalysis B: Environmental

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Section: Effect Of Type and Pre-treatment Of Activated Carbon Supportmentioning

confidence: 99%

K-promoted NiMo catalysts supported on activated carbon for the hydrogenation reaction of CO to higher alcohols: Effect of support and active metal

Liakakou

Heracleous

Triantafyllidis

et al. 2015

Applied Catalysis B: Environmental

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“…A comparison of this catalyst's performance and similar bulk catalysts reported in Woo et al (1991) and Liu et al (1997) is shown in Table 4.2. While the test conditions for the three catalysts are not the same, it appears that the catalyst reported in this study has comparable reactivity.…”

Section: Molybdenum Sulfide-based Catalystmentioning

confidence: 99%

Mixed Alcohol Synthesis Catalyst Screening

Gerber¹,

White²,

Stevens³

2007

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SummaryThe Department of Energy's (DOE) Pacific Northwest National Laboratory (PNNL) and National Renewable Energy Laboratory (NREL) are conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). PNNL is tasked with obtaining commercially available mixed alcohol or preparing promising mixed-alcohol catalysts and screening them in a laboratory-scale reactor system. Commercially available catalysts and the most promising experimental catalysts are provided to NREL for testing using a slipstream from a pilot-scale biomass gasifier.After a review of the literature and conversations with companies that produce catalysts, it was determined that commercial, mixed alcohols synthesis catalysts are not currently available. One catalyst manufacturer did supply a modified methanol catalyst (MeOH-X). This catalyst was tested in the PNNL laboratory-scale system and provided to NREL for further testing. ICI Katalco (ICI) provided a commercially available methanol catalyst that was also tested at PNNL and provided to NREL to evaluate the performance of both catalyst testing systems PNNL also prepared and tested the behavior of 10 other catalysts representing the distinct catalyst classes for mixed alcohol syntheses. The test conditions and the range of C 2 + oxygenate space-time yields (STYs) for these 10 catalysts plus the ICI and MeOH-X catalysts are shown in Table S.1. (a) C 2 + oxygenates were predominantly C 2 to C 5 alcohols, acetic acid, acetaldehyde, and ethyl acetate.The Rh/Mn/Fe/SiO 2 catalyst and the two Fischer-Tropsch-based catalysts had significantly higher C 2 + oxygenate STYs than any of the other catalysts, including the MeOH-X catalyst. However, there are other considerations that must be used to fairly compare the catalysts. Specifically, it was found that in no cases were C 2 + oxygenates the major product. Methanol and/or Fischer-Tropsch liquids were major coproducts for all but the Rh/Mn/SiO 2 and Rh/Mn/Fe/SiO 2 catalysts. It was also found that the reactor iv system was subject to exothermic excursions under conditions that produced the high STYs for the two Fischer-Tropsch catalysts and nearly so for the rhodium catalyst. Tests that achieved the highest C 2 + oxygenate STY for each catalyst were compared in terms of the STYs of all liquid products, including C 1 oxygenates, C 2 + alcohols, other C 2 + oxygenates, and Fisher-Tropsch liquids, as shown in Figure S.1. Also shown are the liquid product STYs for the same Fischer-Tropsch catalyst under conditions that produce a lower C 2 + oxygenate STY that provides a fairer comparison to the other catalysts.The MeOH-X catalyst can be economic because the high-methanol STY falls within the recommended range for commercial methanol plants that were selected according to Stiles et al. (1991). The Rh/Mn/Fe/SiO 2 catalyst produces high a C 2 + oxygenate STY but, because it does not produce other coproducts in significant quantities, it does not achieve the minimum recommended STY based on a methanol ...

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“…Molybdenum carbide in particular has shown catalytic activity for conversion of syngas to hydrocarbons and alcohols [14,15,16,17,18,19,20,8,21,22], steam/dry reforming [6,18,3,10,23,24,25], water-gas shift [26,27,28], methane aromatization [7,29,30], hydrocarbon hydrogenolysis [6,19,14,18], hydrocarbon hydrogenation [8,31,32] and various other reactions involving hydrocarbons and alcohols [8,33,30,34,35]. The activity and selectivity of molybdenum carbide differs depending on the synthesis procedure and reaction conditions [17], and can be tuned using alkali metal promoters such as potassium or rubidium [36,37]. In order to further improve the performance of molybdenum carbide catalysts it is of value to understand the reactivity, selectivity, and stability of molybdenum carbide under various conditions.…”

Section: Introductionmentioning

confidence: 99%

Elementary steps of syngas reactions on Mo2C(001): Adsorption thermochemistry and bond dissociation

Medford

Vojvodić

Studt

et al. 2012

Journal of Catalysis

102

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Density functional theory (DFT) and ab initio thermodynamics are applied in order to investigate the most stable surface and subsurface terminations of Mo 2 C(001) as a function of chemical potential and in the presence of syngas. The Mo-terminated (001) surface is then used as a model surface to evaluate the thermochemistry and energetic barriers for key elementary steps in syngas reactions. Adsorbtion energy scaling relations and Brønsted-Evans-Polanyi relationships are established and used to place Mo 2 C into the context of transition metal surfaces. The results indicate that the surface termination is a complex function of reaction conditions and kinetics. It is predicted that the surface will be covered by either C 2 H 2 or O depending on conditions. Comparisons to transition metals indicate that the Mo-terminated Mo 2 C(001) surface exhibits carbon reactivity similar to transition metals such as Ru and Ir, but is significantly more reactive towards oxygen.

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Mixed alcohol synthesis from carbon monoxide and dihydrogen over potassium-promoted molybdenum carbide catalysts

Cited by 153 publications

References 18 publications

K-promoted NiMo catalysts supported on activated carbon for the hydrogenation reaction of CO to higher alcohols: Effect of support and active metal

K-promoted NiMo catalysts supported on activated carbon for the hydrogenation reaction of CO to higher alcohols: Effect of support and active metal

Mixed Alcohol Synthesis Catalyst Screening

Elementary steps of syngas reactions on Mo2C(001): Adsorption thermochemistry and bond dissociation

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