Synthesis and characterization of gallium-based perovskite-type dense membrane with oxygen semipermeability

La0.15Sr0.85Ga0.3Fe0.7O3-delta (LSGFO) and La0.15Sr0.85Co0.3Fe0.7O3-delta (LSCFO) mixed oxygen-ion and electron conducting oxides were synthesized by using a combined EDTA and citrate complexing method, and the corresponding dense membranes were fabricated. The properties of the oxide powders and membranes were characterized with combined SEM, XRD, H-2-TPR, O-2-TPD techniques, mechanical strength and oxygen permeation measurement. The results showed that LSGFO had much higher thermochemical stability than LSCFO due to the higher valence stability of Ga3+. After the temperature-programmed reduction by 5% H-2 in Ar from 20 degreesC to 1020 degreesC, the basic perovskite structure of LSGFO was successfully preserved. LSGFO also favors the oxygen vacancy formation better than LSCFO. Oxygen permeation measurement demonstrated that LSGFO had higher oxygen permeation flux than LSCFO, but they had similar activation energy for oxygen transportation, with a value of 110 and 117 kJ . mol(-1), respectively The difference in oxygen permeation fluxes was correlated with the difference in oxygen vacancy concentrations for the two materials.

Synthesis of titanium silicalites in different template systems and their catalytic performance

Titanium silicalites have been synthesized in the TPABr+ammonia, TPABr+hexanediamine, TPABr+ethylenediamine, TPABr+diethylamine, TPABr+TEAOH, TPABr+n-butylamine, TPABr+TBAOH and TBAOH+n-butylamine systems. As-synthesized titanium silicalites were characterized by XRD, IR and C-13 CP MAS NMR. Catalytic performance in epoxidation of propylene and template effect was investigated. It has been shown that both TPABr and TBAOH serve as templating agent in TPABr+TBAOH system. But in other systems, when there is enough TPABr, organic amines or ammoniums only act as the bases. TEAOH or n-butylamine can take the role of template when less TPABr is added. It indicates that the ability of organic amines or ammoniums to direct the Pentasil structure decreases as follows: TPA(+)>TBA(+)>TEA(+)>n-butylamine. Catalysts exhibiting good performance in epoxidation of propylene can be attained using TPABr as the template and ammonia, n-butylamine, diethylamine, hexanediamine or TBAOH as bases. (C) 1999 Elsevier Science B.V. All rights reserved.

Surface structure and reaction performances of highly dispersed and supported bimetallic catalysts

Surface structures of Pt-Sn and Pt-Fe bimetallic catalysts have been investigated by means of Mossbauer spectroscopy, Pt-L-III -edge EXAFS and H-2-adsorption. The results showed that the second component, such as Sn or Fe, remained in the oxidative state and dispersed on the gamma-Al2O3 surface after reduction, while Pt was completely reduced to the metallic state and dispersed on either the metal oxide surface or the gamma-Al2O3 surface. By correlating the distribution of Pt species on different surfaces with the reaction and adsorption performances, it is proposed that two kinds of active Pt species existed on the surfaces of both catalysts, named M-1 sites and M-2 sites. M-1 sites are the sites in which Pr directly anchored on the gamma-Al2O3 surface, while M-2 sites are those in which Pt anchored on the metal oxide surface. M-1 sites are favorable for low temperature H-2 adsorption, and responsible for the hydrogenolysis reaction and carbon deposition, while M-2 sites which adsorb more H-2 at higher temperature, are more resistant to the deactivation due to less carbon deposition, and provide major contribution to the dehydrogenation reaction.

Titanium species in titanium silicalite TS-1 prepared by hydrothermal method

The titanium species existing in titanium silicalite TS-1, which is prepared by hydrothermal method, were investigated using chemical analysis, XRD, FT-IR, Si-29 MAS NMR, UV-VIS, ESR. It has been observed that several kinds of titanium species may exist in titanium silicalite. The form that titanium atoms incorporate into the framework of titanium silicalite synthesized using tetrapropylammonium bromide (TPABr) as template differs from that using the classical method. But, the symmetry of titanium silicalite, changes from monoclinic to orthorhombic with the increase of titanium content in both methods. The Ti-O-2(-) originated from framework titanium and H2O2 has the moderate stability and may be active site in oxidation reaction. TS-1 synthesized using TPABr as template does not contain anatase, but contains a kind of partly condensed titanium species with six-fold coordination. The titanium species may correspond to 270-280 mn band in UV-VIS spectra and also can form Ti-O-2(-). But, this kind of Ti-O-2(-) is very stable and cannot be catalytic active site. So, the six-fold coordination titanium species may be inactive in both the oxidation reaction and the decomposition of H2O2. The hypothesis has been further proved by the phenomena that the titanium species is easily washed off using acid, and acid treating will not influence the catalytic performance of TS-1. (C) 2001 Elsevier Science B.V. All rights reserved.

Partial oxidation of methane over the perovskite oxides

Ba0.5Sr0.5Co0.8Fe0.2O3-delta and Ba0.5Sr0.5Co0.8Ti0.2O3-delta oxides were synthesized by a combined EDTA-citrate complexing method. The catalytic behavior of these two oxides with the perovskite structure was studied during the reaction of methane oxidation. The pre-treatment with methane has different effect on the catalytic activities of both the oxides. The methane pre-treatment has not resulted in the change of the catalytic activity of BSCFO owing to its excellent reversibility of the perovskite structure resulting from the excellent synergistic interaction between Co and Fe in the oxide. However, the substitution with Ti on Fe-site in the lattice makes the methane pre-treatment have an obvious influence on the activity of the formed BSCTO oxide.

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.

Synthesis of zeolite NaA membranes with high permeance under microwave radiation on mesoporous-layer-modified macroporous substrates for gas separation

This article reported the NaA zeolite membranes with high permeance synthesized with microwave heating method under different conditions: (1) on a macroporous substrate in gel, (11) on a mesoporous/macroporous (top-mesoporous-layer-modified macroporous) substrate in gel, and (111) on a mesoporous/macroporous substrate in sol. In general, the H-2 permeance of the NaA membranes by microwave heating in gel was usually at the level of 10(-6) mol s(-1) m(-2) Pa-1, much higher than that by the conventional hydrothermal synthesis. At similar H-2/C3H8 permselectivity. On the substrate modified mesoporous top layer, the H-2 permeance of the NaA membranes by microwave heating in gel or sol was further enhanced, while maintaining comparable H-2/C3H8 permselectivity, due to the prevention of penetration of the reagent into the pores of the macroporous substrate. Meanwhile, the synthesis took less time in sol than in gel on the mesoporous/macroporous substrate. The NaA membranes synthesized in sol had larger permeance than those in gel and underwent transformation in shorter time. The permeation of C3H8 suggested that there existed unwanted intercrystalline pores or defects in the membranes. © 2005 Elsevier B.V. All rights reserved.

Real-time investigation of the photodissociation dynamics of p-chlorotoluene and p-dichlorobenzene

De-excited dynamics of p-chlorotoluene and p-dichlorobenzene have been investigated by the femtosecond pump-probe method in a supersonic molecular beam. The yields of the parent ion and daughter ion are examined as a function of the delay time between the pump and probe laser pulses. The lifetime constants of excited p-chlorotoluene and p-dichlorobenzene are determined. Possible de-excitation mechanisms are suggested that the initially excited S-1 state is predissociative via the repulsive triplet state. The substituent effects of additional chlorine atom and methyl group are discussed. Moreover, for the first time, we observe a novel quantum beat oscillation in p-dichlorobenzene. (c) 2005 Elsevier B.V. All rights reserved.

Development and application of oxygen permeable membrane in selective oxidation of light alkanes

In this paper, oxygen permeable membrane used in membrane reactor for selective oxidation of alkanes will be discussed in detail. The recent developments for the membrane materials will be presented, and the strategy for the selection of the membrane materials will be outlined. The main applications of oxygen permeable membrane in selective oxidation of light alkanes will be summarized, which includes partial oxidation of methane (POM) to syngas and partial oxidation of heptane (POH) to produce H-2, oxidative coupling of methane (OCM) to C-2, oxidative dehydrogenation of ethane (ODE) to ethylene and oxidative dehydrogenation of propane (ODP) to propylene. Achievements for the membrane material developments and selective oxidation of light alkanes in membrane reactor in our group are highlighted.

Ligand modified real heterogeneous catalysts for fixed-bed hydroformylation of propylene

A novel ligand modified heterogeneous catalyst has been developed for hydroformylation of propylene, which showed excellent activity, selectivity and stability and need not be separated from the product after reaction in a fixed-bed reactor. The coordination bonds between triphenyl phosphine (PPh3) and Rh/SiO2 were confirmed by means of thermogravimetric (TG), solid-state P-31 NMR, XPS and FT-IR. Two types of active species for hydroformylation were formed, which were proved by in situ FT-IR techniques. The problem of metal leaching was greatly reduced by directly fastening Rh particles on the support, and the active Rh species that was responsible for the outstanding performance of propylene hydroformylation was tightly bound by the very strong metal-metal bonds. No sign of deactivation was observed over a period of more than 1000 h on the condition that PPh3 was added at 300-350 h of time on stream. (c) 2005 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.

Hydroisomerization of long-chain alkane over Pt/SAPO-11 catalysts synthesized from nonaqueous media

SAPO-11 molecular sieves were synthesized from nonaqueous media. The effects of Si and Al sources as well as solvents on the catalytic performance of SAPO-11 were investigated by the hydroisomerization reaction of n-dodecane. The samples were characterized by XRD, XRF, N-2-adsorption, SEM, NH3-TPD, IR-NH3 and Si-29 CP MAS NMR. The SAPO-11 samples synthesized with tetraethoxysilane as the Si source showed higher Si incorporation contents than the SAPO molecular sieves prepared with polymeric Si sources (fumed silica and Si colloidal gel). The reaction results showed that Pt/SAPO-11 catalysts synthesized from ethylene glycol and glycerol media with the monomeric Si and Al sources (tetraethoxysilane, aluminum isopropoxide) exhibited higher catalytic activities than those catalysts with the polymeric Si or Al (pseudo-boehmite) sources, due to the larger external surface area and higher acidity of the former ones. Especially, the catalyst synthesized in an ethylene glycol medium possessed the highest catalytic activity. Over this catalyst, 88% conversion of n-dodecane was achieved at a low temperature of 250 degrees C.