Rh/C catalysts in ethene hydroformylation: the effect of different supports and pretreatments

Kainulainen, T.A.; Niemelä, Marita; Krause, A.O.I.

doi:10.1016/s1381-1169(98)00223-4

Cited by 23 publications

(6 citation statements)

References 40 publications

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“…Hydroformylation of ethylene is usually associated with model studies in gas-phase reactions using metals on supports or metal oxides . A serious side-reaction under these conditions is the hydrogenation of CO that produces methanol and C 2 oxygenates.…”

Section: Substrates and Reactionsmentioning

confidence: 99%

Applied Hydroformylation

2012

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Section: Substrates and Reactionsmentioning

confidence: 99%

Applied Hydroformylation

2012

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“…In recent years, there has been growing research interest in developing catalysts with activated-carbon (AC) supports for several types of reactions, because of the low cost, unique texture, and surface properties of the ACs. Reactions include hydrogenation, − oxidation, − hydrodenitrogenation (HDN), hydrodesulfurization (HDS), − hydroformylation, and methanol decomposition . Transition metals (Fe, Co, Mo, and Cu) and noble metals (Pt, Ru, and Rh) have been found to be effective for these reactions. ,,,,,,− Because AC materials are relatively inexpensive and are known to have high surface areas, broad ranges of pore size distribution (PSD), and complex surface chemistry, many studies have focused on the effects of the physical and chemical properties of carbons on the performance of the carbon-supported catalysts. ,,, It was reported that the physical texture of AC (e.g., properties such as surface area and porosity) remarkably impacts reduction and dispersion of active metals on the AC surface, especially when the conventional incipient-wetness impregnation (IWI) technique is used.…”

Section: Introductionmentioning

confidence: 99%

“…Catal. 2001, 208, 35-46. (5) Choi, J. S. hydrodesulfurization (HDS), [9][10][11][12] hydroformylation, 13 and methanol decomposition. 14 Transition metals (Fe, Co, Mo, and Cu) and noble metals (Pt, Ru, and Rh) have been found to be effective for these reactions.…”

Section: Introductionmentioning

confidence: 99%

Effect of Properties of Various Activated-Carbon Supports and Supported Fe−Mo−Cu−K Catalysts on Metal Precursor Distribution, Metal Reduction, and Fischer−Tropsch Synthesis

Kugler

Dadyburjor

2010

Energy Fuels

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The physical and surface chemistry properties of four activated carbons (ACs) have been studied, and the effects of these properties on the distribution and reduction of metal precursors of Fischer−Tropsch (FT) catalysts have been noted. The four ACs used have been derived from peat, generic wood, pecan, and walnut. The catalysts used are Fe with Mo−Cu−K additives, supported on the various ACs, successfully used earlier for selective production of C1−C34 hydrocarbons. Characterization techniques used include Brunauer−Emmett−Teller (BET), scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), surface pH, temperature-programmed desorption−mass spectrometry (TPD−MS), transmission electron microscopy (TEM), and temperature-programmed reduction (TPR). The BET and SEM results show that the four ACs have similar overall pore-size distributions qualitatively. All ACs contain 75−94% micropores. The four ACs differ considerably in their surface morphology, surface area, and amounts of micro-, meso-, and macropores. The AC derived from peat is the least porous. ACs derived from pecan and walnut show ridges containing small spherical agglomerates. These ACs contain relatively more meso- and macropores (wide pores) than the wood AC, which has a wide distribution of irregular agglomerates. The EDS result indicates that all four ACs contain 5.6−7.5% oxygen; the wood- and peat-based varieties include smaller amounts of other impurities as well. The results of pH and TPD indicate that the surface of all four ACs are primarily covered by neutral and/or basic oxygen-containing groups, along with small amounts of acidic oxygen groups. Analyzing the BET, TPD, and TEM results of the four carbon-supported Fe−Mo−Cu−K catalysts shows that metal precursors are uniformly distributed on each AC surface, but the distribution of metal precursors on the carbon surface is likely related to pore types and amounts and not the total surface area of supports. Wide pores play a more important role to distribute metal precursors than micropores. Metal precursors tend to be present predominantly inside the pores of the peat-, pecan-, and walnut-based ACs, which contain greater amounts of wide pores. However, for the wood-based AC, which contains greater amounts of micropores, more metal precursors tend to be present on the exterior surface and the average metal particle size is also larger. The TPR and BET results indicate that the interaction between metallic precursors and the AC surface appears to be associated with both the chemical nature of the AC support and size of metal precursors. TPR and TPD indicate that stronger interactions between metal precursors and supports are observed on the peat-based ACs, with more neutral or basic oxygen-containing groups and smaller metal sizes, and the weakest interactions are observed on the wood-based AC support. The large particles on the exterior of the wood-based AC surface likely weaken the interaction. All four catalysts were used in FT reactions. Estimated values of the turnover freq...

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“…The reason for cobalt catalyst was chosen due not only to its low cost but also to its high activity. Active carbon has been shown to exhibit beneficial characteristics as the strong support for active metal as well as the excellent hydroformylation activity and oxygenate selectivity. − …”

Section: Introductionmentioning

confidence: 99%

Low-Pressure Hydroformylation of Middle Olefins over Co and Rh Supported on Active Carbon Catalysts

Asami

et al. 2003

Energy Fuels

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The hydroformylation of olefin has been investigated on Co and Rh catalysts supported on active carbon at mild reaction conditions (403 K, 3.0 MPa) in the slurry phase reactor. Of the catalysts, Co/activated carbon catalysts showed excellent catalytic performance only in the alcoholic solvent, while Rh/activated carbon catalyst exhibited good activity in the nonpolar solvent. Rh/activated carbon catalyst showed stable activity for 14 h in the continuous feeding system, giving the total turnover number of 500. The effects of solvents were discussed in detail. The details of reaction conditions that affected the performance of the catalysts have been optimized. The higher catalytic activity was found at the lower temperature, about 403 K. About 20% of metal was dissolved from the support, a determination based on inductively coupled plasma (ICP) atomic emission spectrometry. The dissolved part was thought to deposit again on the support and work as active species as well.

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Rh/C catalysts in ethene hydroformylation: the effect of different supports and pretreatments

Cited by 23 publications

References 40 publications

Applied Hydroformylation

Applied Hydroformylation

Effect of Properties of Various Activated-Carbon Supports and Supported Fe−Mo−Cu−K Catalysts on Metal Precursor Distribution, Metal Reduction, and Fischer−Tropsch Synthesis

Low-Pressure Hydroformylation of Middle Olefins over Co and Rh Supported on Active Carbon Catalysts

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