Complete hydrodechlorination of chlorobenzene and its derivatives over supported nickel catalysts under liquid phase conditions

Liquid phase hydrodechlorination of chlorobenzene was studied over Ni/active carbon (Ni/AC), Ni/gamma-Al2O3, Ni/SiO2 and Raney Ni. The complete hydrodechlorination of chlorobenzene was realized at 333-343 K on Ni/AC under hydrogen atmosphere of 1.0 MPa in the presence of alkaline hydroxide. Aryl halides, three chlorotoluenes (o-, m- and p-), three chloroanilines, three chlorobenzotrifluorides, three dichlorobenzenes and two trichlorobenzenes (1,2,3- and 1,2,4-) were also completely hydrodechlorinated under the similar conditions. Chlorobenzene derivatives having either an electron-donating group or an electron-withdrawing group decreased their reactivities with respect to the unsubstituted chlorobenzene.

Preparation and characterization of multi-walled carbon nanotubes supported PtRu catalysts for proton exchange membrane fuel cells

A series of PtRu nanocomposites supported on H2O2-oxidized multi-walled carbon nanotubes (MWCNTs) were synthesized via two chemical reduction methods - one used aqueous formaldehyde (HCHO method) and the other used ethylene glycol (EG method) as the reducing agents. The effects of the solvents (water and ethylene glycol) and the surface composition of the MWCNTs on the deposition and the dispersion of the metal particles were investigated using N-2 adsorption. TEM. ICP-AES. FTIR and TPD. The wetting heats of the MWCNTs in corresponding solvents were also measured. The characterizations suggest that combination of the surface chemistry of the MWCNTs with the solvents decides the deposition and the dispersion of the metal nanoparticles. These nanocomposites were evaluated as proton exchange membrane fuel cell anode catalyts for oxidation of 50 ppm CO contaminated hydrogen and compared with a commercial PtRu/C catalyst. The data reveal superior performances for the nanocomposites prepared by the EG method to those by the HCHO method and even to that for tile Commercial analogue. Structure performance relationship of the nanocomposites was also studied. (C) 2005 Elsevier Ltd. All rights reserved.

Enhancement of the catalytic performance of supported-metal catalysts by pretreatment of the support

We report an interesting finding that the catalytic performance of supported Ag/SiO2 catalysts toward selective catalytic oxidation of CO in hydrogen at low temperatures can be greatly enhanced by pretreatment of the SiO2 support before catalyst preparation. Calcination of SiO2 at appropriate temperatures preferentially removes the H-bonded SiOH, which results in the highly dispersive Ag/SiO2 catalyst and thus improves the catalytic performance. (c) 2005 Elsevier Inc. All rights reserved.

The effect of Rh particle size on the catalytic performance of porous silica supported rhodium catalysts for CO hydrogenation

Silica-supported Rh catalysts with different Rh particle dimensions were investigated for CO hydrogenation. The catalysts were characterized by various techniques such as TEM, H-2-TPR and N-2 adsorption to study the catalyst morphology, the size distributions of Rh particles and the silica pores. It was found that the distribution and the size of Rh particles were affected by the silica pores, and the metal grains were enclosed in the pores of the support, and thereby their growth was limited. The catalytic activity and selectivity to C-2-oxygenates for CO hydrogenation were found to be significantly controlled by the Rh particle sizes, and the higher activity and selectivity to C2-oxygenates were obtained over bigger Rh particles, within the range of the reported particle sizes.

Gasoline-range hydrocarbon synthesis over cobalt-based Fischer-Tropsch catalysts supported onSiO2/HZSM-5

Two types of SiO2 with different mesopore size and HZSM-5 zeolite were used to prepare hybrid supported cobalt-based catalysts. The textual and structural properties of the catalysts were studied using N-2 physisorption, X-ray diffraction (XRD), and H-2 temperature-programmed reduction (TPR) techniques. Fischer-Tropsch synthesis (FTS) performances of the catalysts were carried out in a fixed-bed reactor. The combination effects of the meso- and micropores of the supports as well as the interaction between supports and cobalt particles on FTS activity are discussed. The results indicate that the catalyst supported on the tailor-made SiO2 and HZSM-5 hybrid maintained both meso- and micropore pores during the preparation process without HZSM-5 particles agglomerating. The mesopores provided quick mass transfer channels, while the micropores contributed to high metal dispersion and accelerated hydrocracking/hydroisomerization reaction rate. High CO conversion of 83.9% and selectivity to gasoline-range hydrocarbons (C-5-C-12) of 55%, including more than 10% isoparaffins, were achieved simultaneously on this type of catalyst.

On the induction period of methane aromatization over Mo-based catalysts

The behavior of different species during the temperature-programmed surface reaction (TPSR) of methane over various catalysts is traced by an online mass spectrometer, It is demonstrated that the transformation of MoO3 to molybdenum carbide hinders the activation of methane as well as the succeeding aromatization in the TPSR, If this transformation process is done before the reaction, the temperature needed for methane activation and benzene formation will be greatly lowered (760 and 847 K, respectively). On the basis of comparison of the catalytic behavior of molybdenum supported on different zeolites, it is suggested that the initial activation of methane is the rate-determining step of this reaction. For the cobalt catalysts supported on HMCM-22 or Mo catalysts supported on TiO2, no benzene formation could be observed during the TPSR, However, the prohibition of benzene formation is different in nature over these two catalysts: the former lacks the special properties exhibited by molybdenum carbide, which can continuously activate methane even when multiple layers of carbonaceous species are formed on its surface, while the latter cannot accomplish the aromatization reaction since there are no Bronsted acid sites to which the activated intermediates can migrate, although the activation of methane can be achieved on it. Only for the catalysts that possess both of these properties, together with the special channel structure of zeolite, can efficient methane aromatization be accomplished. (C) 2000 Academic Press.

Isobutane/butene alkylation over supported heteropoly acid catalysts: I. Influence of the structure of silica

Catalysts consisting of heteropoly acids (HPAs) supported on different silica and mesoporous molecular sieves have been prepared by impregnation and the sol-gel method, respectively, and their catalytic behavior in fixed-bed alkylation of isobutane with butene has been investigated. The activity, selectivity and stability of the supported-HPA catalysts could be correlated with the surface acidity of the catalysts, the structure of supports as well as the time on stream (TOS). In the fixed-bed reactor, the acidity of the heteropoly acid is favorable to the formation of dimerization products (C-8(=)); especially, the pore size of supports was seen to have an important effect on activity and product distribution of the catalysts. Contrary to the traditional solid-acid catalysts, the supported-HPA catalysts own an excellent stability for alkylation, which makes it possible for these supported catalysts to replace the liquid-acid catalysts used in industry.

FACTORS AFFECTING THE ROLE OF SIO2 IN MGCL2-SUPPORTED ZIEGLER-NATTA COPOLYMERIZATION CATALYSTS

This paper describes the roles of silica (SiO2), the butoxy ligand (-OBu) and ethyl benzoate (EB) on ethylene/1-butene copolymerization with MgCl2/SiO2-supported titanium catalysts. The distribution of SiO2 and of the elements Mg and Ti was observed by means of an energy-dispersed X-ray microanalyzer on a scanning electron microscope (SEM). An inversed Si/Mg ratio results, at invariant Ti/Mg ratio and -OBu content, in higher catalyst efficiency and higher comonomer incorporation, with a correspondingly decreased crystallinity of the copolymers. Thus, the inert carrier SiO2 favors copolymerizability, as seen from the values of the reactivity ratios. The copolymer compositional distribution is also affected by the SiO2 content, as seen from the DSC curves of the copolymers. As to the copolymer morphology, addition of SiO2 makes the copolymer particles larger and more uniform.

A study on reduction behaviors of the supported platinum-iron catalysts

The reduction behaviors of the supported platinum-iron catalysts and their comparison with supported iron catalysts were studied by TPR (temperature-programmed reduction)-in situ Fe-57 MBS (Mossbauer spectroscopy). The results indicated that the TPR processes of all Fe-containing catalysts were different from that of bulk alpha-Fe2O3. There were interactions between Pt, Fe and the gamma-Al2O3 or SiO2 support for the Pt-Fe/gamma-Al2O3 and Pt-Fe/SiO2 catalysts. All the iron-containing catalysts show that Fe3+ was highly dispersed on the support (gamma-Al2O3 and SiO2) before reduction. No Fe-0 was found in the reduction processes. The Fe3+ was reduced to Fe2+ in tetrahedral vacancy first for the reduction of the Pt-Fe/gamma-Al2O3 catalyst. No Fe2+ in octahedral vacancy was found in the reduction of the Pt-Fe/SiO2 catalyst. Adding Pt to Fe/support (gamma-Al2O3 or SiO2) could promote the reduction of the Fe species. (C) 1999 Elsevier Science B.V. All rights reserved.