Different mechanisms for the formation of acetaldehyde and ethanol on the Rh-based catalysts

Different mechanisms for the formation of acetaldehyde and ethanol on the Rh-based catalysts were investigated by the TPR (temperature programmed reaction) method, and the active sites were studied by CO-TPD, TPSR (temperature programmed surface reaction of preadsorbed CO by H-2) and XPS techniques. The TPR results indicated that ethanol and acetaldehyde might be formed through different intermediates, whereas ethanol and methanol might result from the same intermediate. Results of CO-TPD, TPSR, and XPS showed that on the Rh-based catalyst, the structure of the active sites for the formation of C-2-oxygenates is ((RhxRhy+)-Rh-0)-O-Mn+ (M=Mn or Zr, x>>y, 2 less than or equal ton less than or equal to4). The tilt-adsorbed CO species is the main precursor for CO dissociation and the precursor for the formation of ethanol and methanol. Most of the linear and geminal adsorbed CO species desorbed below 500 K. Based on the suggested model of the active sites, detailed mechanisms for the formation of acetaldehyde and ethanol are proposed. Ethanol is formed by direct hydrogenation of the tilt-adsorbed CO molecules, followed by CH2 insertion into the surface CH2-O species and the succeeding hydrogenation step. Acetaldehyde is formed through CO insertion into the surface CH3-Rh species followed by hydrogenation, and the role of the promoters was to stabilize the intermediate of the surface acetyl species. (C) 2000 Academic Press.

Modeling of a compact plate-fin reformer for methanol steam reforming in fuel cell systems

The characteristics of a compact plate-fin reformer (PFR) which integrates endothermic and exothermic reactions into one unit have been investigated by experiment as well as by numerical simulation. One reforming chamber was integrated with two vaporization chambers and two combustion chambers to constitute a single unit of PFR. In the PFR, which is based on a plate-fin beat exchanger, catalytic combustion of the reforming gas is used to simulate the fuel cell anode off gas (AOG) which supplies the necessary heat for the methanol steam reforming. Temperature distributions in all chambers and composition distribution in reforming chamber have been studied, and the effect of the ratio of H2O/CH3OH on the performance of the PFR has also been investigated. A model of the PFR was derived using a three-dimensional numerical model for a cross-current flow arrangement. Theoretical predictions of the temperature distributions in the PFR were in good agreement with experimental values. In addition, the numerical model was able to accurately predict the methanol conversion and the reformate composition in reforming chamber. © 2005 Elsevier B.V. All rights reserved.

Mixed reforming of heptane to syngas in the Ba0.5Sr0.5Co0.8Fe0.2O3 membrane reactor

Fuel cells are recognized as the most promising new power generation technology, but hydrogen supply is still a problem. In our previous work, we have developed a LiLaNiO/gamma-Al2O3 catalyst, which is excellent not only for partial oxidation of hydrocarbons, but also for steam reforming and autothermal reforming. However, the reaction needs pure oxygen or air as oxidant. We have developed a dense oxygen permeable membrane Ba0.5Sr0.5Co0.8Fe0.2O3 which has an oxygen permeation flux around 11.5 ml/cm(2) min at reaction conditions. Therefore, this work is to combine the oxygen permeable membrane with the catalyst LiLaNiO/gamma-Al2O3 in a membrane reactor for hydrogen production by mixed reforming of heptane. Under optimized reaction conditions, a heptane conversion of 100%, a CO selectivity of 91-93% and a H-2 selectivity of 95-97% have been achieved. (c) 2005 Elsevier B.V. All rights reserved.

The role of Sn in Pt-Sn/CeO2 catalysts for the complete oxidation of ethanol

The structural features and catalytic properties of Pt-Sn/CeO2 catalysts prepared by modified polyol method were extensively investigated for the complete oxidation of ethanol. CO chemisorption, TPR, DTA and XPS measurements identically indicated that the electronic configuration of Pt by Sn as well as the formation of PtSn alloy were the key factors in determining the nature of the active sites, A strong Pt/Sn atomic ratio dependence of catalytic perfortmances was observed. which was explained in terms of the change., in the Surface structure of metal phases and the electronic Pt-Sn interaction. (c) 2005 Elsevier B.V. All rights reserved.

Physicochemical properties of silk fibroin after solubilization using calcium chloride with or without ethanol

To elucidate the physicochemical properties of silk protein, we studied the effects of calcium chloride and ethanol on the gelation of fibroin. Fibroin was treated with 5.0 M calcium chloride in water (Ca/W) or 5.0 M calcium chloride in 20% (v/v) ethanol (Ca/Et) and the rheological properties of colloidal fibroin were investigated. The Ca/W-treatment promoted an increased rate of gelation and gave higher gel strength than the Ca/Et-treatment. The maximum gel strengths of Ca/W- and Ca/Et-treated fibroins were obtained at pH 7.0 and pH 5.5, respectively. Scanning electron micrographs showed that the Ca/W-treated fibroin gel had a more developed three-dimensional molecular network than the Ca/Et-treated gel. Further, FT-IR spectra suggested that Ca/W-treated fibroin has more of a beta-structure than Ca/Et-treated one in colloidal conditions. This study indicated that the use of calcium chloride alone was more beneficial to the gelation of fibroin than combined use with ethanol.

One-step synthesis of 2-pentanone from ethanol over K-Pd/MnOx-ZrO2-ZnO catalyst

A highly active and selective K-Pd/MnOx-ZrO2-ZnO catalyst for the one-step synthesis of 2-pentanone from ethanol is described. The possible reaction pathways for ethanol reaction over K-Pd/MnOx-ZrO2-ZnO catalyst were investigated by means of TPSR, CO2- and NH3-TPD techniques. The reactions were performed in a fixed bed continuous flow reactor. Complete conversion with high selectivity for 2-pentanone, was observed under 370 similar to 390degreesC, 2 similar to 4 MPa, GHSV = 8000 similar to 10,000 h(-1) and LHSV < 1.25 h(-1) conditions. Ethanol reactions over K-Pd/MnOx-ZrO2-ZnO catalyst showed that the catalyst could catalyze dehydrogenation. aldol. dehydration and hydrogenation reactions. Both acidic and basic properties are found on the surface of K-Pd/MnOx-ZrO2-ZnO catalyst, whose multifunctionality with the combination of basic, acid and metal sites may be responsible for the efficiency of the K-PdMnOx-ZrO2-ZnO catalyst. (C) 2004 Elsevier B.V. All rights reserved.

Methanol steam reforming in a compact plate-fin reformer for fuel-cell systems

A compact plate-fin reformer (PFR) consisting of closely spaced plate-fins, in which endothermic and exothermic reactions take place in alternate chambers, has been studied. In the PFR, which was based on a plate-fin heat exchanger, catalytic combustion of the reforming gas, as a simulation of the fuel cell anode off gas (AOG), supplied the necessary heat for the reforming reaction. One reforming chamber, which was for hydrogen production, was integrated with two vaporization chambers and two combustion chambers to constitute a single unit of PFR. The PFR is very compact, easy to be placed and scaled up. The effect of the ratio of H2O/CH3OH on the performance of the PFR has been investigated, and temperature distributions in different chambers were studied. Besides, the stationary behavior of the PFR was also investigated. Heat transfer of the reformer was enhanced by internal plate-fins as well as by external catalytic combustion, which offer both high methanol conversion ratio and low CO concentration. In addition, the fully integrated reformer exhibited good test stability. Based on the PFR, a scale-up reformer was designed and operated continuously for 1000 h, with high methanol conversion ratio and low CO concentration. (c) 2004 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Autothermal reforming of n-octane on Ru-based catalysts

In an attempt to effectively integrate catalytic partial oxidation (CPO) and steam reforming (SR) reactions on the same catalyst, autothermal reforming (ATR) of n-octane was addressed based on thermodynamic analysis and carried out on a non-pyrophoric catalyst 0.3 wt.% Ru/K2O-CeO2/gamma-Al2O3. The ATR of n-octane was more efficient at the molar ratio Of O-2/C 0.35-0.45 and H2O/C 1.6-2.2 (independent parameters), respectively, and reforming temperature of 750-800 degrees C (dependent parameter). Among the sophisticated reaction network, the main reaction thread was deducted as: long-chain hydrocarbon -> CH4, short-chain hydrocarbon -> CO2, CO and H-2 formation by steam reforming, although the parallel CPO, decomposition and reverse water gas shift reaction took place on the same catalyst. Low temperature and high steam partial pressure had more positive effect on CH4 SR to produce CO2 other than CO. This was verified by the tendency of the outlet reformate to the equilibrium at different operation conditions. Furthermore, the loss of active components and the formation of stable but less active components in the catalyst in the harsh ATR atmosphere firstly make the CO inhibition capability suffer, then eventually aggravated the ATR performance, which was verified by the characterizations of X-ray fluorescence, BET specific surface areas and temperature programmed reduction. (c) 2005 Elsevier B.V. All rights reserved.