Microwave-assisted hydrothermal synthesis of hydroxy-sodalite zeolite membrane

A high quality pure hydroxy-sodalite zeolite membrane was successfully synthesized on an alpha-Al2O3 support by a novel microwave-assisted hydrothermal synthesis (MARS) method. Influence of synthesis conditions, such as synthesis time, synthesis procedure, etc., on the formation of hydroxy-sodalite zeolite membrane by MAHS method was studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and gas permeation measurements. The synthesis of hydroxy-sodalite zeolite membrane by MAHS method only needed 45 min and synthesis was more than 8 times faster than by the conventional hydrothermal synthesis (CHS) method. A pure hydroxy-sodalite zeolite membrane was easily synthesized by MAHS method, while a zeolite membrane, which consisted of NaX zeolite, NaA zeolite and hydroxy-sodalite zeolite, was usually synthesized by CHS method. The effect of preparation procedures had a dramatic impact on the formation of hydroxy-sodalite zeolite membrane and a single-stage synthesis procedure produced a pure hydroxy-sodalite zeolite membrane. The pure hydroxy-sodalite zeolite membrane synthesized by MARS method was found to be well inter-grown and the thickness of the membrane was 6-7 mum. Gas permeation results showed that the hydrogen/n-butane permselectivity of the hydroxy-sodalite zeolite membrane was larger than 1000. (C) 2004 Elsevier Inc. All rights reserved.

Synthesis and properties of A-type zeolite membranes by secondary growth method with vacuum seeding

A-type zeolite membranes were successfully synthesized on tubular alpha-Al2O3 supports by secondary growth method with vacuum seeding In the seeding process, a thin, uniform and continuous seeding layer was closely attached to the support surface by the pressure difference between the two sides of the support wall. The effects of seed particle size, suspension concentration, coating pressure difference and coating time on the membrane and its pervaporation properties were investigated. The as-synthesized membranes were characterized by XRD and SEM. The quality of the membranes was evaluated by the pervaporation dehydration of 95 wt. % isopropanol/water mixture at 343 K. High quality A-type zeolite membranes can be reproducibly prepared by the secondary growth method with vacuum seeding under the conditions: seed particle size of 500-1200 nm, suspension concentration of 4-8 g/l, coating pressure difference of 0.0100-0.0250 MPa and coating time of 45-180 s. (C) 2004 Elsevier B.V. All rights reserved.

Liquid-phase hydrodechlorination of chlorinated benzenes over active carbon supported nickel catalysts under mild conditions

Liquid phase hydrodechlorination of chlorinated benzenes was studied over Ni/active carbon (Ni/AC), Ni/gamma-Al2O3, Ni/SiO2 and Raney Ni. The complete dechlorination of chlorobenzene (ClBz) was realized at 333-343 K on Ni/AC under hydrogen atmosphere of 1.0 MPa in the presence of alkaline hydroxide. Dichloro- and trichlorobenzenes were also hydrodechlorinated with 50-95% yields of benzene under the similar conditions, as above. The reaction follows zero-order to ClBz concentration and 1.9 order to hydrogen pressure. The reaction does not proceed in the absence of alkaline hydroxide, suggesting the complete coverage of active nickel surface with produced chlorine and the removal of the chlorine ion with hydroxide ion as a rate-limiting step. The active catalysts were characterized by H-2 chemisorption and transmission electron microscopy techniques. The apparent activity strongly depends on the active area of nickel on catalyst surface. (C) 2004 Published by Elsevier B.V.

Effect of support on chromium based catalysts for the oxidative dehydrogenation of C2H6 with CO2 to C2H4

The oxidative dehydrogenation of ethane (ODE) with CO2 to C2H4 has been studied over a series of Cr-based catalysts using SiO2, Al2O3, (MCM-41 zeolite) MCM-41, MgO and Silicate-2 (Si-2) as the supports. TPR, NH3-TPD, and EPR characterizations of catalysts were carried out to investigate the reduction property of Cr species on different supports, the acidities of catalysts and Cr species of 6Cr/SiO2 catalysts, respectively.

沉积物中典型氧化物矿物吸附的镉对芦苇的生物有效性研究

选用沉积物中5种典型氧化物矿物:针铁矿、磁铁矿、三水铝石、氧化铝、二氧化锰,以水培法和单一矿物吸附Cd为培养介质,以芦苇为受试植物,研究环境中不同化学形态Cd(即吸附在不同矿物表面)的生物有效性差别.经过45 d的培养,发现矿物吸附的Cd被芦苇吸收富集,不同形态Cd的富集强度不同,根组织富集量72.70~320.44 mg.kg-1,并遵循以下规律:Al(OH)3>Al2O3>Fe3O4>MnO2>FeOOH.Cd的富集特征反映了不同矿物吸附Cd能力和稳定性的差异,通过采用3种低分子量有机酸对Cd的解吸,评价了这几种矿物对镉的吸附强度.结果表明,Cd的解吸量遵循如下规律,乙酸、苹果酸:Al(OH)3>Fe3O4>Al2O3>FeOOH>MnO2;柠檬酸:Al(OH)3>Al2O3>Fe3O4>FeOOH>MnO2,这与芦苇对各种矿物吸附镉的富集程度顺序基本一致.Cd的化学形态是影响其生物有效性的重要因素.

Promotional effect of colloidal alumina on the activity of the In/HZSM-5 catalyst for the selective reduction of NO with methane

Colloidal alumina was used to improve the activity of an In/HZSM-5 catalyst for the selective reduction of NO with CH4 in the excess of oxygen. Compared with In/HZSM-5, the In/HZSM-5/Al2O3 catalyst showed higher activity in a wide range of reaction temperatures. It is visualized that a synergetic effect between In/HZSM-5 and Al2O3 enhances the conversion of NOx. The addition of Al2O3 improved the conversion of NO to NO2 and facilitated the activation of methane. An In/HZSM-5/Al2O3 pre-treated with steam for 15 h at 700 degreesC still showed a high activity for the removal of NOx with methane, while an In/HZSM-5 similarly pre-treated with steam showed a lower activity than the fresh sample. The activity of the In/HZSM-5/Al2O3 catalyst could be restored completely after water vapor was removed from the feed gas. Furthermore, it was found that the In/HZSM-5/Al2O3 remained fairly active under high GHSV and O-2 concentration conditions. It was also interesting to find that an increase in NO content could enhance the conversion of methane, and this illustrates that the existence of NO is beneficial for the activation of methane. (C) 2002 Elsevier Science B.V. All rights reserved.

In situ IR spectroscopic studies on molybdenum nitride catalysts: active sites and surface reactions

Recent IR spectroscopic studies on the surface properties of fresh Mo2N/gamma-Al2O3 catalyst are presented in this paper. The surface sites of fresh Mo2N/gamma-Al2O3, both Modelta+ (0<δ<2) and N sites, are probed by CO adsorption. Two characteristic IR bands were observed at 2045 and 2200 cm(-1), due to linearly adsorbed CO on Mo and N sites, respectively. The surface N sites are highly reactive and can react with adsorbed CO to form NCO species. Unlike adsorbed CO on reduced passivated one, the adsorbed CO on fresh Mo2N/gamma-Al2O3 behaves similarly to that of group VIII metals, suggesting that fresh nitride resembles noble metals. It is found that the surface of Mo nitrides slowly transformed into sulfide under hydrotreating conditions, which could be the main reason for the activity drop of molybdenum nitride catalysts in the presence of sulfur-containing species. Some surface reactions, such as selective hydrogenation of 1,3-butadiene, isomerization of 1-butene, and hydrodesulfurization of thiophene, were studied on both fresh and reduced passivated Mo2N/gammaAl(2)O(3) catalysts using IR spectroscopy. The mechanisms of these reactions are proposed. The adsorption and reaction behaviors of these molecules on fresh molybdenum nitride also resemble those on noble metals, manifesting the unique properties of fresh molybdenum nitride catalysts. Mo and N sites are found to play different roles in the adsorption and catalytic reactions on the fresh Mo2N/gammaAl(2)O(3) catalyst. Generally, Mo sites are the main active sites for the adsorption and reactions of adsorbates; N sites are not directly involved in catalytic reactions but they modify the electronic properties of Mo sites.

Identifying the isolated transition metal ions/oxides in molecular sieves and on oxide supports by UV resonance Raman spectroscopy

Isolated transition metal ions/oxides in molecular sieves and on surfaces are a class of active sites for selective oxidation of hydrocarbons. Identifying the active sites and their coordination structure is vital to understanding their essential role played in catalysis and designing and synthesizing more active and selective catalysts. The isolated transition metal ions in the framework of molecular sieves (e.g., TS-1, Fe-ZSM-5, and V-MCM-41) or on the surface of oxides (e.g., MoO3/Al2O3 and TiO2/SiO2) were successfully identified by UV resonance Raman spectroscopy. The charge transfer transitions between the transition metal ions and the oxygen anions are excited by a UV laser and consequently the UV resonance Raman effect greatly enhances the Raman signals of the isolated transition metal ions. The local coordination of these ions in the rigid framework of molecular sieves or in the relatively flexible structure on the surface can also be differentiated by the shifts of the resonance Raman bands. The relative concentration of the isolated transition metal ion/oxides could be estimated by the intensity ratio of Raman bands. This study demonstrates that the UV resonance Raman spectroscopy is a general technique that can be widely applied to the in-situ characterization of catalyst synthesis and catalytic reactions. (C) 2003 Elsevier Science (USA). All rights reserved.

Carbon monoxide adsorption on molybdenum phosphides: Fourier transform infrared spectroscopic and density functional theory studies

Molybdenum phosphide (MoP) and supported molybdenum phosphide (MoP/gamma-Al2O3) have been prepared by the temperature-programmed reduction method. The surface sites of the MoP/gamma-Al2O3 catalyst were characterized by carbon monoxide (CO) adsorption with in situ Fourier transform infrared (FT-IR) spectroscopy. A characteristic IR band at 2037 cm(-1) was observed on the MoP/gamma-Al2O3 that was reduced at 973 K. This band is attributed to linearly adsorbed CO on Mo atoms of the MoP surface and is similar to IR bands at 2040-2060 cm(-1), which correspond to CO that has been adsorbed on some noble metals, such as platinum, palladium, and rhodium. Density functional calculations of the structure of molybdenum phosphides, as well as CO chemisorption on the MoP(001) surface, have also been studied on periodic surface models, using the generalized gradient approximation (GGA) for the exchange-correlation functional. The results show that the chemisorption of CO on MoP occurred mainly on top of molybdenum, because the bonding of CO requires a localized mininum potential energy. The adsorption energy obtained is DeltaH(ads) approximate to -2.18 eV, and the vibrational frequency of CO is 2047 cm-1, which is in good agreement with the IR result of CO chernisorption on MoP/gamma-Al2O3.

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.

Performance of palladium-containing supported catalysts in the oxidation of 1-butene

Performance of palladium-containing supported catalysts in the oxidation of 1-butene was investigated in a fixed-bed flow microreactor. The Pd-Fe-HCl/Ti-Al catalyst is the best among the five Pd-Fe-HCl/X (A = SiO2, gamma-Al2O3, Al-Ti, TiO2, MCM-22) catalysts for the oxidation of I-butene to butanone. It is interesting that high propionic acid selectivity can be obtained when V and H2SO4 are added to the palladium-containing supported catalysts.

Heat capacities and thermodynamic functions of p-chlorobenzoic acid

The heat capacities of p-chlorobenzoic acid were measured in the temperature range from 80 to 580 K by means of an automatic adiabatic calorimeter equipped with a small sample cell of internal volume of 7.4cm(3). The construction and procedures of the calorimetric system were described in detail. The performance of this calorimetric apparatus was evaluated by heat capacity measurements on alpha-Al2O3. The deviations of experimental heat capacities from the corresponding smoothed values lie within +/-0.28 per cent, while the inaccuracy is within +/-0.40 per cent, compared with the recommended reference data in the whole experimental temperature range. A fusion transition at T = 512.280 K was found from the C-p-T curve of p-chlorobenzoic acid. The enthalpy and entropy of the phase transition, as well as the thermodynamic functions {G((T)) - G((298.15))}, {H-(T) - H-(298.15)} and {S-(T) - S-298.15}, were derived from the heat capacity data. The mass fraction purity of p-chlorobenzoic acid sample used in the present calorimetric study was determined to be 0.99935 by fraction melting approach. (C) 2002 Elsevier Science Ltd. All rights reserved.

Improvement of Pt catalyst for soot oxidation using mixed oxide as a support

Catalytic activity of Pt catalysts for soot oxidation was studied using temperature programmed reactions. The activity of Pt loaded over TiO2-SiO2 (Pt/TiO2-SiO2) showed higher activity than other Pt/MOx systems (MOx = TiO2, ZrO2, SiO2, Al2O3. TiO2-ZrO2. TiO2-Al2O3, ZrO2-SiO2, ZrO2-Al2O3, SiO2-Al2O3). The activity was highest when the molar ratio of TiO2/(TiO2 + SiO2) ranged from 0.4 to 0.7. The effect of pretreatment with a gas containing low SO2 concentrations on the activity was compared for Pt/SiO2, Pt/TiO2 and Pt/TiO2-SiO2. In the case of Pt/TiO2-SiO2, the activity was markedly promoted by the pretreatment whereas no variation in the activity was observed for Pt/SiO2. The difference in the behavior towards the SO, pretreatment was attributed to property difference in the supports for sulfate accumulation. The high activity of Pt/TiO2-SiO2 was also confirmed under practical conditions with a diesel engine exhaust using a catalyst-supported diesel particulate filter (DPF). (C) 2003 Elsevier Science B.V. All rights reserved.

The experimental research for production of hydrogen from n-octane through partially oxidizing and steam reforming method

The reaction of producing hydrogen for fuel cell which used normal octane as gasoline or diesel oil reactant through catalytic partial oxidizing and steam reforming method has been researched in the fixed-bed reactor. A series of catalysts that mainly used nickel supported on Al2O3 have been studied. It showed that the activity of the catalyst was increased with the content of nickel by using only nickel supported on Al2O3. However, its activity was not obviously increased when the content of nickel was over 5 wt%. The conversion ratio of normal octane and hydrogen selectivity were higher at higher reaction temperature. The single noble catalyst of palladium had better stability compared with that of platinum catalyst although their activity and selectivity were similar during the experimental reaction temperature. The prepared bimetallic catalyst consisted mainly of nickel and little noble metal of palladium supported on Al2O3. It showed that this catalyst had higher activity and selectivity, especially at lower or higher reaction temperatures compared with single nickel or palladium catalyst, and better stability. ((C) 2001 International Association for Hydrogen Energy. Published by Elsevier Science Ltd. All rights reserved.

Catalytic decomposition of hydrazine over supported molybdenum nitride catalysts in a monopropellant thruster

The catalytic decomposition of hydrazine over a series of MoNx/gamma-Al2O3 catalysts with different Mo loadings was investigated in a monopropellant thruster (10 N). When the Mo loading is equal to or higher than the monolayer coverage of MoO3 on gamma-Al2O3, the catalytic performance of the supported molybdenum nitride catalyst is close to that of the conventionally used Ir/gamma-Al2O3 catalyst. The MoNx/gamma-Al2O3 catalyst with a loading of about 23wt% Mo (1.5 monolayers) shows the highest activity for hydrazine decomposition. There is an activation process for the MoNx/gamma-Al2O3 catalysts at the early stage of hydrazine decomposition, which is probably due to the reduction of the oxide layer formed in the passivation procedure.