Activity of RhNaX catalysts promoted by transition-metal oxides in the carbonylation of methanol with carbon monoxide at atmospheric pressure

Nefëdov, B. K.; Dzhaparidze, R. V.; Mamaev, O. G.; Сергеева, Н. С.

doi:10.1007/bf00925881

Cited by 2 publications

(2 citation statements)

References 3 publications

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“…Only a very limited number of studies have investigated solid catalysts for ethanol carbonylation to propionic acid or ethyl propionate, and all are for group VIII metals promoted with alkyl iodides [15][16][17][18]. Both Nefedov and Scurrell separately showed that Rh supported on X-type zeolites are effective heterogeneous catalysts for vapor-phase alcohol carbonylation with added iodide [15][16][17][18][19][20][21][22]. Rh has also been supported on various materials including carbon [23,24] or ligand-modified oxides [25] for carbonylation of methanol in the vapor phase.…”

Section: Introductionmentioning

confidence: 99%

Vapor-phase ethanol carbonylation with heteropolyacid-supported Rh

Yacob

Park

Kilos

et al. 2015

Journal of Catalysis

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a b s t r a c tEthanol carbonylation is a potential route to valuable C3 products. Here, Rh supported on porous, Cs-exchanged heteropolyacid Cs 3 PW 12 O 40, is demonstrated as an effective catalyst for vapor-phase ethanol carbonylation, with higher selectivity and conversion to propionates than existing catalysts. Residual acidity or a Mo polyatom was strongly detrimental to yields. Propionate selectivity was maximized at 96% at 170°C and with added H 2 O. The catalyst displayed stable selectivity over 30 h on stream and up to 77% conversion. Ethyl iodide is a required co-catalyst but at levels as low as 2% relative to ethanol. XPS and in situ XANES indicate partial Rh reduction, consistent with the formation of low-valent reactive intermediates and slow deactivation through formation of Rh nanoparticles. With further optimization and understanding, these Rh/heteropolyacid catalysts may lead to stable and selective catalysts for the production of propionates through ethanol carbonylation.

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Section: Introductionmentioning

confidence: 99%

Vapor-phase ethanol carbonylation with heteropolyacid-supported Rh

Yacob

Park

Kilos

et al. 2015

Journal of Catalysis

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“…Prior methanol carbonylation work has shown that Rh supported on a type-X zeolite is an effective heterogeneous catalyst in the presence of a methyl iodide co-feed. [6][7][8][9][10][11] Beyond the Rh/X system, there have been numerous supports investigated specifically for Rh-catalyzed carbonylation, including various zeolites [12][13][14][15], silica [10], alumina [16,17], heteropolyacids [18], carbon [19,20], and polymers [21,22].…”

Section: Introductionmentioning

confidence: 99%

Vapor phase ethanol carbonylation over Rh supported on zeolite 13X

Yacob

Kilos

Barton

et al. 2016

Applied Catalysis A: General

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While methanol carbonylation has been extensively studied, higher alcohol carbonylation has received relatively little attention, even though, for example, ethanol carbonylation could be a useful route for the production of propionates. Here we use Rh/Na13X to investigate the vapor phase carbonylation of ethanol with an ethyl iodide co-feed. In the base case, the catalyst is ~40% selective to propionates, with the remainder forming ethylene and diethyl ether. Deposition of additional alkali can increase selectivities to ~60%. Isotopic labeling of ethyl iodide demonstrates reversible formation of ethyl iodide from ethanol, and that preferential incorporation of ethyl iodide initiates the Rh-catalyzed carbonylation cycle. XPS and in situ X-ray absorption spectroscopy are consistent an active anionic Rh I iodide species at a zeolite exchange site. This proposed structure and the attendant catalytic reaction network are directly analogous to those of classic solution-phase Rh catalysts and other supported Rh catalysts. However, important differences are noted in the reaction orders and apparent activation barrier, which suggest that the rate of ethyl iodide formation is overall rate limiting under these conditions and for this catalyst.

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Activity of RhNaX catalysts promoted by transition-metal oxides in the carbonylation of methanol with carbon monoxide at atmospheric pressure

Cited by 2 publications

References 3 publications

Vapor-phase ethanol carbonylation with heteropolyacid-supported Rh

Vapor-phase ethanol carbonylation with heteropolyacid-supported Rh

Vapor phase ethanol carbonylation over Rh supported on zeolite 13X

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