Effect of pore ring number of zeolites on catalytic performance of Mo/Zeolite in methane aromatization under non-oxygen condition

The catalytic behavior of Mo-based zeolite catalysts with different pore structure and size, particularly with 8 membered ring ( M R), 10 M R, coexisted 10 and 12 M R, and 12 M R, was studied in methane aromatization under the conditions of SV=1500 ml/(g.h), p=0.1 MPa and T = 973 K. It was found that the catalytic performance is correlated with the pore structure of the zeolite supports. The zeolites that possess 10 MR or 10 and 12 MR pore structure with a pore diameter equal to or slightly larger than the dynamic diameter of benzene molecule, such as ZSM-5, ZSM-11, ZRP-1 and MCM-22, are fine supports. Among the tested zeolite supports, MCM-22 exhibits the highest activity and selectivity for benzene. A methane conversion of 10.5% with benzene selectivity of 80% was achieved over Mo/MCM-22 catalyst. The Mo/ERS-7 catalyst with 8 MR (0.45 nm) does not show any activity in methane dehydro-aromatization, while Mo/JQX-1 and Mo/SBA-15 catalysts with 12 MR pore exhibit little activity in the reaction. It can be concluded that the zeolites with 10 MR pore or coexisted 10 and 12 MR, having pore size equal to or slightly larger than the dynamic diameter of benzene molecule, are fine supports for methane activation and aromatization.

Partial oxidation of ethane to syngas in an oxygen-permeable membrane reactor

A perovskite-type oxide of Ba0.5Sr0.5Co0.8Fe0.2O3-delta (BSCFO) with mixed electronic and oxygen ionic conductivity at high temperatures was used as an oxygen-permeable membrane. A tubular membrane of BSCFO made by extrusion method has been used in the membrane reactor to exclusively transport oxygen for the partial oxidation of ethane (POE) to syngas with catalyst of LiLaNiO/gamma-Al2O3 at temperatures of 800-900 degreesC. After only 30 min POE reaction in the membrane reactor, the oxygen permeation flux reached at 8.2 ml cm(-2) min(-1). After that, the oxygen permeation flux increased slowly and it took 12 h to reach at 11.0 ml cm(-2) min(-1). SEM and EDS analysis showed that Sr and Ba segregations occurred on the used membrane surface exposed to air while Co slightly enriched on the membrane surface exposed to ethane. The oxygen permeation flux increased with increasing of concentration of C2H6, which was attributed to increasing of the driving force resulting from the more reducing conditions produced with an increase of concentration of C2H6 in the feed gas. The tubular membrane reactor was successfully operated for POE reaction at 875 degreesC for more than 100 h without failure, with ethane conversion of similar to 100%, CO selectivity of >91% and oxygen permeation fluxes of 10-11 ml cm(-2) min(-1). (C) 2002 Elsevier Science B.V. All rights reserved.

Methane dehydro-aromatization over a Mo/phosphoric rare earth-containing penta-sil type zeolite in the absence of oxygen

The dehydro-aromatization of methane over a Mo-modified penta-sil type high-silica zeolite containing phosphoric and rare earth oxide (abbreviated as Mo/HZRP-1) was investigated. As a modification of HZSM-5, HZRP-1 is also a good support for the preparation of Mo-based zeolite catalysts, and is active for methane dehydro-aromatization. Mo/HZRP-1 catalysts are more active at high Mo loadings compared with Mo/HZSM-5 catalysts. Al-27 MAS NMR spectra of Mo/HZRP-1 reveal that there are two kinds of framework Al in HZRP-1. It is suggested that only the tetrahedral coordinated Al atoms in the form of Al-O-Si species in the zeolite, in the proton forms, are responsible for the formation of aromatics.

Perovskite-type B-site Bi-doped ceramic membranes for oxygen separation

Novel mixed conducting oxides, B-site Bi-doped perovskites were exploited and synthesized. Cubic perovskite structures were formed for BaBi0.2COyFe0.8-yO3-delta (y less than or equal to 0.4) and BaBixCo0.2Fe0.8-xP3-delta (x=0.1-0.5) The materials exhibited considerable high oxygen permeability at high temperature. The oxygen permeation flux of BaBi0.2Co0.35Fe0.45O3-delta membrane reached about 0.77 x 10(-6) mol/cm(2) s under an air/helium oxygen partial pressure gradient at 900 degrees C, which was much higher than that of other bismuth-contained mixed conducting membranes. The permeation fluxes of the materials increased with the increase of cobalt content, but no apparent simple relationship was found with the bismuth content. The materials also demonstrated excellent reversibility of oxygen adsorption and desorption. Stable time-related oxygen permeation fluxes were found for BaBi0.2CO0.35Fe0.45O3-delta and BaBi0.3Co0.2Fe0.5O3-delta a membranes at 875 degrees C.

Syngas production using an oxygen-permeating membrane reactor with cofeed of methane and carbon dioxide

CH4-CO2-O-2 reforming to syngas in a never Ba0.5Sr0.5Co0.8Fe0.2O3.delta oxygen-permeable membrane reactor using LiLaNiO/gamma-Al2O3 as catalyst was successfully reported. Excellent reaction performance was achieved with around 92% methane conversion efficiency, 95% CO2 conversion rate, and nearly 8.5mL/min.cm(2) oxygen permeation flux. In contrast to the oxygen permeation model with the presence of large concentration of CO2 (under such condition the oxygen permeation flux deteriorates with time), the oxygen permeation flux is really stable under the CH4CO2-O-2 reforming condition.

Easy fabrication of dense ceramic membrane for oxygen separation

A combined EDTA-citrate complexing method was developed for the easy preparation of mixed oxygen-ionic and electronic conducting dense ceramic membrane for oxygen separation. The nea method takes the advantage of lower calcination temperature for phase formation. lower membrane sintering temperature and higher relative density over the standard ceramic method.