On the surface sites Of MOP/SiO2 catalyst under sulfiding conditions: IR spectroscopy and catalytic reactivity studies

The surface sites of MoP/SiO2 catalysts and their evolution under sulfiding conditions were characterized by IR spectroscopy using CO as the probe molecule. The HDS activities of thiophene were measured on the MoP/SiO2 catalyst that was subjected to different sulfidation and reactivation pretreatments. Cus Modelta+ (0 < delta less than or equal to 2) sites are probed on the surface of fresh MoP/SiO2 by molecularly adsorbed CO, exhibiting a characteristic IR band at 2045 cm(-1). The surface of MoP/SiO2 is gradually sulfided in HDS reactions, as revealed by the shift of the IR band at 2045 to ca. 2100 cm(-1). Although the surface of a MoP/SiO2 catalyst becomes partially sulfided, the HDS activity tests show that MoP/SiO2 is fairly stable in the initial stage of the HDS reaction, providing further evidence that molybdenum phosphide is a promising catalytic material for industrial HDS reactions. Two kinds of surface sulfur species are formed on the sulfided catalyst: reversibly and irreversibly bonded sulfur species. The MoP/SiO2 catalyst remains stable in the HDS of thiophene because most sulfur species formed under HDS conditions are reversibly bonded on the catalyst surface. A detrimental effect of presulfidation on the HDS activity is observed for the MoP/SiO2 catalyst treated by H2S/H-2 at temperatures higher than 623 K, which is ascribed to the formation of a large amount of the irreversibly bonded sulfur species. The irreversibly sulfided catalyst can be completely regenerated by an oxidation and a subsequent reduction under mild conditions. (C) 2003 Elsevier Inc. All rights reserved.

Membrane cartridges for endotoxin removal from interferon preparations

The suitability of membrane cartridges for the removal of endotoxin from both distilled water and interferon preparations was examined. The endotoxin concentrations were reduced to 4.0 and 7.3 EU/ml, respectively, when about 4000 ml of distilled water with 20 and 28 EU/ml were passed through the deoxycholate and chitosan immobilized membrane cartridges. When 200 ml of interferon preparation with endotoxin concentration more than 80 EU/ml and pH 3.9 were applied to a deoxycholate immobilized membrane cartridge at a flow-rate of 9 ml/min, the endotoxin concentration was reduced to less than 10 EU/ml. However, if an interferon preparation of 450 ml, with more than 80 EU/ml of endotoxin and pH 3.9 was applied to the chitosan immobilized membrane cartridge at a flow-rate of 18 ml/min, the endotoxin concentration was reduced to less than 10 EU/ml. (C) 2003 Elsevier Science B.V. All rights reserved.

Correlation between the characteristics and catalytic performance of Ni-V-O catalysts in oxidative dehydrogenation of propane

Ni - V - O series catalysts for the oxidative dehydrogenation (ODH) of propane were prepared and characterized by BET, XRD, H-2- TPR, O-2-TPD-MS and electrical conductivity. At 425 degreesC a C3H6 selectivity of 49.9% was observed on Ni0.9V0.1OY at a C3H8 conversion of 19.4%, and the obtained selectivity is almost two times higher than that over NiO at the roughly same conversion of C3H8. The mobile oxygen species created by the interaction of NiO and V2O5 has been found in the composite catalysts by O-2-TPD-MS and electrical conductivity studies, which seems to be responsible for the enhanced selectivity of the propane oxidative dehydrogenation.

Synthesis of novel P-ketimine bidentate ferrocenyl ligands with central and planar chirality and comparsion in the catalytic activity between P-ketimine and P-aldimine

A series of novel ferrocenylphosphine-ketimine ligands 6 were prepared by reaction of (R,S-p)-PPFNH2-R or (S,S-p)-PPFNH2 with a variety of m-substituted acetophenones. A different catalytic activity was observed between ferrocenylphosphine-ketimine ligands and corresponding aldimine ligands. The efficiency and diastereomeric impact of these ferrocenylphosphine-ketimine ligands in Pd-catalyzed asymmetric allylic alkylation were first investigated, and higher enantioselectivity of over 98% e.e. with 95% yield was obtained by the use of ferrocenylphosphine-ketimine ligands. However, in Rh-catalyzed asymmetric hydrosilylation of aryl ketones, only 42% e.e. was obtained by the use of ferrocenylphosphine-ketimine ligands compared to 90% e.e. with the use of aldimine ligands. (C) 2003 Elsevier Ltd. All rights reserved.

Reduction property and catalytic activity of Ce1-XNiXO2 mixed oxide catalysts for CH4 oxidation

Ce1-XNiXO2 oxides with X varying from 0.05 to 0.5 were prepared by different methods and characterized by XRD and TPR techniques. Ce(0.7)Mi(0.3)O(2) sample prepared by sol-gel method shows the highest reducibility and the highest catalytic activity for methane combustion. Three kinds of Ni phases co-exist in the Ce1-XNiXO2 catalysts prepared by sol-gel method: (i) aggregated NiO on the support CeO2, (ii) highly dispersed NiO with strong interaction with CeO2 and (iii) Ni atoms incorporated into CeO2 lattice. The distribution of different Ni species strongly depends on the preparation methods. The highly dispersed NiO shows the highest activity for methane combustion. The NiO aggregated on the support CeO2 shows lower catalytic activity for methane combustion, while the least catalytic activity is found for the Ni species incorporated into CeO2. Any oxygen vacancy formed in CeO2 lattice due to the incorporating of Ni atoms adsorbs and activates the molecular oxygen to form active oxygen species. So the highest catalytic activity for methane combustion on Ce0.7Ni0.3O2 catalyst is attributed not only to the highly dispersed Ni species but also to the more active oxygen species formed. (C) 2002 Elsevier Science B.V. All rights reserved.

Post-steam-treatment of Mo/HZSM-5 catalysts: An alternative and effective approach for enhancing their catalytic performances of methane dehydroaromatization

Post-steam-treatment is a facile and effective method for improving the catalytic performances of Mo/HZSM-5 catalysts in methane dehydroaromatization under nonoxidative conditions. The treatment can enhance the stability of the catalyst and also give a higher methane conversion and a higher yield of light aromatics, as well as a decrease in the formation rate of carbonaceous deposits. (27)Al, (29)Si, and (1)H multinuclear magic angle spinning nuclear magnetic resonance, X-ray photoelectron spectroscopy, X-ray diffraction, X-ray fluorescence spectroscopy, and thermogravimetric analysis measurements as well as catalytic reaction evaluations were employed to conduct comparative studies on the properties of the catalysts before and after the post-steam-treatment. The results revealed that the number of free Bronsted acid sites per unit cell decreased, while more Mo species migrated into the HZSM-5 channels for the 6Mo/HZSM-5 catalysts after the post-steam-treatment. In addition, the average pore diameter was also larger for the post-steam-treated catalysts, and this was advantageous for mass transport of the reaction products. However, a severe post-steam-treatment, i.e., with longer treating time, of the 6Mo/HZSM-5 catalyst will lead to the formation of the Al(2)(MoO(4))(3) phases, which is detrimental to the reaction.

Catalytic partial oxidation of n-heptane for hydrogen production

Partial oxidation of n-heptane (POH) for hydrogen generation was studied over several catalysts between 700 and 850degreesC. Modified Ni-based/gamma-Al2O3 catalyst exhibited not only good catalytic activity but also good carbon deposition resistance ability. Under the modified reaction conditions, 100% n-heptane conversion and 93% hydrogen selectivity can be obtained.

Structure and oxygen permeability of a dual-phase membrane

The dual-phase membrane of La0.15Sr0.85Ga0.3Fe0.7O3-delta-Ba0.5Sr0.5Fe0.2Co0.8O3-delta (LSGF-BSCF) was prepared successfully. This membrane was characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM) and electron probe micro-analyzer (EPMA). This membrane has a dense dual-phase structure: LSGF being the dense body of this membrane and BSCF as another phase running along the LSGF body. This structure is favorable for the oxygen permeation through the membrane. The oxygen permeation test shows that the oxygen permeation flux of LSGF-BSCF membrane (Jo(2) = 0.45 ml/min cm(2), at 915 degreesC) is much higher than that of LSGF membrane (Jo(2) = 0.05 ml/min cm(2)). Thickness dependence of oxygen permeation indicates that the oxygen permeation is controlled by the bulk diffusion. Compared to pure BSCF the dual-phase membrane of LSGF-BSCF is stable in reducing atmosphere. (C) 2003 Elsevier B.V. All rights reserved.

Oxidative dehydrogenation of propane in a dense tubular membrane reactor

Oxidative dehydrogenation of propane (ODP) to propylene was investigated in a dense tubular membrane reactor made of Ba0.5Sr0.5Co0.8Fe0.2O3-delta (BSCF) at 700degreesC and 750degreesC. The propylene selectivity in the membrane reactor (44.2%) is much higher than that in the fixed-bed reactor (15%) at the similar propane conversion (23-27%). Higher propylene selectivity in the membrane reactor was attributed to the lattice oxygen (O2-) supplied through the membrane.