Selective hydroformylation of ethylene on rhodium-zinc-silica. An apparent example of site isolation of rhodium and Lewis acid-promoted carbonyl insertion

Ichikawa, Masaru; Lang, A. J.; Shriver, Duward F.; Sachtler, W. M. H.

doi:10.1021/ja00310a098

Cited by 91 publications

(30 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Research reported by Sachtler and Ichikawa (1986) and Ichikawa et al (1985) suggests that when small amounts of base metals such as zinc are added to a Rh/SiO 2 catalyst, the ethylene added to a H 2 /CO synthesis gas is preferentially converted into predominantly propionic aldehyde instead of ethane. This suggests that there are opportunities to improve the yields of C 3 + oxygenates using the rhodium and Fischer-Tropsch catalysts by adding promoters that increase hydroformylation of olefins present in the product gas in significant concentrations.…”

Section: Conclusion and Recommendationsmentioning

confidence: 99%

Mixed Alcohol Synthesis Catalyst Screening

Gerber¹,

White²,

Stevens³

2007

View full text Add to dashboard Cite

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 ...

show abstract

Section: Conclusion and Recommendationsmentioning

confidence: 99%

Mixed Alcohol Synthesis Catalyst Screening

Gerber¹,

White²,

Stevens³

2007

View full text Add to dashboard Cite

show abstract

“…The catalytic performances in heterogeneous catalysis are generally improved by addition of various promoters, such as, Zn, Se, Na, etc. [1][2][3][4][5]. However, the activities and selectivity of the heterogeneous Rh-Zn/SiO 2 , Rh-Ag/SiO 2 catalyst are still much lower.…”

Section: Introductionmentioning

confidence: 99%

The PPh3 ligand modified Rh/SiO2 catalyst for hydroformylation of olefins

Zhu¹,

Ding²,

Li³

et al. 2004

Catalysis Today

View full text Add to dashboard Cite

“…The presence of tin atoms regularly distributed on the platinum surface isolates the platinum atoms by increasing the distance between two adjacent platinum atoms, as do the copper atoms on a nickel surface [222] or the tin atoms on a rhodium, platinum or nickel surface [33,118,223,224] . The presence of tin thus avoids the hydrogenolysis reaction, leading to a more selective catalyst.…”

Section: Dehydrogenation Of Isobutane To Isobutenementioning

confidence: 99%