Catalytic conversion of synthesis gas to methanol and other oxygenated products

Stiles, Alvin B.; Chen, Fanglin; Harrison, Jeffrey B.; Hu, Xiaodong; Storm, David A.; Yang, H. X.

doi:10.1021/ie00053a002

Cited by 76 publications

(71 citation statements)

References 9 publications

(11 reference statements)

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“…The primary screening and selection criterion for catalyst performance was the 1.2 space-time yield (STY) of C 2 + oxygenated hydrocarbons, with consideration given to the coproduction of methanol and liquid hydrocarbons. While the NREL techno-economic study cited an STY of 250 to 350 g mixed alcohol/L cat /hr as a productivity rate typical of the molybdenum catalysts, this value was considered marginal based on the assessment made by Stiles et al (1991), who stated that methanol synthesis plants ranged from approximately 670 to 1,340 g MeOH /L cat /hr. According to Stiles et al, higher methanol production rates create dissipation requirements that are difficult to manage.…”

Section: Catalyst Performance Requirementsmentioning

confidence: 99%

“…The K/Cu/Zn/Mn/Co/Cr catalyst was based on a methanol catalyst formulation prepared by Stiles et al (1991) that was modified with manganese, cobalt, and chromium to produce a catalyst with a Cu:Mn:Zn:Co:Cr atomic ratio of 0.4:0.1:0.1:0.003:0.06. The catalyst was prepared using appropriate quantities of the metals as nitrates dissolved in deionized (DI) water at a rate of 6.2 mL total nitrate solution/g Cu(NO 3 ) 2 · 6H 2 O.…”

Section: K/cu/zn/mn/co/cr Modified Methanol Catalystmentioning

confidence: 99%

“…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 plant.…”

mentioning

confidence: 99%

“…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 plant.…”

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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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Section: Catalyst Performance Requirementsmentioning

confidence: 99%

Section: K/cu/zn/mn/co/cr Modified Methanol Catalystmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Mixed Alcohol Synthesis Catalyst Screening

Gerber¹,

White²,

Stevens³

2007

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“…The primary screening and selection criterion for catalyst performance was the space-time yield (STY) of C 2 + oxygenated hydrocarbons, with consideration given 1.2 to the coproduction of methanol and liquid hydrocarbons. While the NREL techno-economic study cited an STY of 250 to 350 g mixed alcohol/L cat /hr as a productivity rate typical of the molybdenum catalysts, this value was considered marginal based on the assessment made by Stiles et al (1991), who stated that methanol synthesis plants ranged from approximately 670 to 1,340 g MeOH /L cat /hr. According to Stiles et al, higher methanol production rates create heat dissipation requirements that are difficult to manage.…”

Section: Catalyst Performance Requirementsmentioning

confidence: 99%

Mixed Alcohol Synthesis Catalyst Screening 2007 Progress Report

Gerber¹,

White²,

Gray³

et al. 2007

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SummaryThe U.S. 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 in 2006 and conversations with companies that produced catalysts, it was determined that no commercial mixed-alcohol synthesis catalysts were available at the time. One catalyst manufacturer did supply a modified methanol catalyst that was tested in the PNNL laboratoryscale system and was provided to NREL for further testing. PNNL also prepared and tested the behavior of 10 other catalysts representing the distinct catalyst classes for mixed alcohol syntheses. Based on those results, further testing in 2007 focused on the performance of rhodium-based catalysts. The effects of adding promoters to the rhodium catalysts in addition to the manganese already being used were examined. The test conditions and the range of C 2 + oxygenate space-time yields (STYs) for these catalysts plus the previously tested rhodium-based catalysts are shown in Table S.1. Based on the promoters tested to date, the following general conclusions can be made:Highest C 2 + oxygenate STYs occur between 300° and 325°C where carbon conversion ranges between ~ 25 and 40% (except for the RhMnCu catalyst, which had ~ 9% carbon conversion).Carbon selectivities to C 2 + oxygenates decrease with increasing reaction temperatures because of higher carbon conversion to hydrocarbons.Carbon selectivities of the organics in the aqueous phase to C 2 + alcohols increase with higher reaction temperatures than the other oxygenates present there.The highest carbon selectivity to C 2 + oxygenates occurs at lower reaction temperatures and accompanying lower STYs.iv In addition to these general trends, the test results singled out specific promoters that showed potential for improving the rhodium-based catalysts. The iridium promoter stood out in terms of significantly improving the STY of oxygenates with a maximum observed STY of ~880 g/Lcat/hr, followed by lithium and nickel with observed maximum STYs of 480 g/Lcat/hr. Selectivities to C 2 + oxygenates at the maximum C 2 + oxygenate STYs were 39, 47, and 32%, respectively, under these conditions. Rhenium and copper promoters were relatively unremarkable in terms of STYs.The iron and rhenium promoters both stood out as achieving higher carbon selectivities to C 2 + alcohols with respect to all oxygenates in the aqueous product, followed by copper, with carbon selectivity ratios of 0.64, 0.60, and 0.47, respectively, at conditions in which each achieved its highest C 2 + oxygenate STY. I...

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