Effect of ultrasonic irradiation and /or halogenation on the catalytic performance of γ-Al2O3 for methanol dehydration to dimethyl ether

Dimethyl ether(DME) is amongst one of the most promising alternative,renewable and clean fuels being considered as a future energy carrier.In this study,the comparative catalytic performance of the halogenated γ-Al 2 O 3 prepared from two halogen precursors(ammonium chloride and ammonium fluoride) is presented.The impact of ultrasonic irradiation was evaluated in order to optimize both the halogen precursor for the production of DME from methanol in a fixed bed reactor.The catalysts were characterized by SEM,XRD,BET and NH 3-TPD.Under reaction conditions where the temperature ranged from 200 to 400 ℃ with a WHSV = 15.9 h-1was found that the halogenated catalysts showed higher activity at all reaction temperatures.However,the halogenated alumina catalysts prepared under the effect of ultrasonic irradiation showed higher performance of γ-Al 2 O 3 for DME formation.The chlorinated γ-Al 2 O 3 catalysts showed a higher activity and selectivity for DME production than fluorinated versions.     

Ni/Al2O3 catalysts for CO methanation: Effect of Al2O3 supports calcined at different temperatures

The correlation between phase structures and surface acidity of Al2O3 supports calcined at different temperatures and the catalytic performance of Ni/Al2O3 catalysts in the production of synthetic natural gas(SNG) via CO methanation was systematically investigated. A series of 10 wt% NiO/Al2O3 catalysts were prepared by the conventional impregnation method, and the phase structures and surface acidity of Al2O3 supports were adjusted by calcining the commercial γ-Al2O3 at different temperatures(600–1200 C). CO methanation reaction was carried out in the temperature range of 300–600 C at different weight hourly space velocities(WHSV = 30000 and 120000 mL·g-1h-1) and pressures(0.1 and 3.0 MPa). It was found that high calcination temperature not only led to the growth in Ni particle size, but also weakened the interaction between Ni nanoparticles and Al2O3 supports due to the rapid decrease of the specific surface area and acidity of Al2O3 supports. Interestingly, Ni catalysts supported on Al2O3 calcined at 1200 C(Ni/Al2O3-1200) exhibited the best catalytic activity for CO methanation under different reaction conditions. Lifetime reaction tests also indicated that Ni/Al2O3-1200 was the most active and stable catalyst compared with the other three catalysts, whose supports were calcined at lower temperatures(600, 800 and 1000 C). These findings would therefore be helpful to develop Ni/Al2O3 methanation catalyst for SNG production.     

Rh/ZnO-Al2O3催化剂用于巴豆醛选择性加氢（英文）

Gas phase hydrogenation of crotonaldehyde was performed over 1 wt% Rh/ZnO-Al2O3 catalysts with various Zn/Rh atomic ratios. Monometallic Rh/Al2O3 was also prepared for comparison. The samples were prepared by the successive impregnation of Al2O3 with chlo-ride precursors of zinc and rhodium. The solids have been characterized by H2 chemisorption,temperature-programmed reduction,scanning electron microscopy,and cyclohexane dehydrogenation. Their catalytic behaviour in the gas phase crotonaldehyde hydrogenation reaction after reduction treatment in flowing hydrogen at 723 K was investigated. The relationship between catalytic activity,selectivity for crotyl alcohol,and physicochemical properties of the catalysts was examined. Results obtained showed that the presence of Zn clearly promotes the hydrogenation of the carbonyl bond. The catalyst with Zn/Rh atomic ratio of 5 displayed good catalytic stability and the highest selectivity for crotyl alcohol(70%) along with alloy formation.     

Additive effects of alkaline-earth metals and nickel on the performance of Co/γ-Al_2O_3 in methane catalytic partial oxidation

Nano-sized γ-alumina (γ-Al2O3) was first prepared by a precipitation method. Then, active component of cobalt and a series of alkaline- earth metal promoters or nickel (Ni) with different contents were loaded on the γ-Al2O3 support. The catalysts were characterized by N2 adsorption-desorption, X-ray diffraction (XRD) and thermogravimetry analysis (TGA). The activity and selectivity of the catalysts in catalytic partial oxidation (CPO) of methane have been compared with Co/γ-Al2O3, and it is found that the catalytic activity, selectivity, and stability are enhanced by the addition of alkaline-earth metals and nickel. The optimal loadings of strontium (Sr) and Ni were 6 and 4 wt%, respectively. This finding will be helpful in designing the trimetallic Co-Ni-Sr/γ-Al2O3 catalysts with high performance in CPO of methane.     

γ-Al2O3负载的金溶胶的尺寸效应对CO催化氧化活性的影响

The relationship between particle size and catalytic activity of gold nanoparticle catalysts with γ-Al2O3 as support has been investigated. The catalysts were prepared via the gold sol with different particle sizes by micelle method, and their structures were characterized by HRTEM and XRD, respectively. Furthermore, the catalytic activities were tested by CO oxidation. Experimental results showed that the catalytic activity became much weaker when gold particles were increased from 3.2 to 6.6 nm. Additionally, the particle size was also a key factor to govern catalytic activity with regard to gold supported on TiO2 prepared by the methods of deposition-precipitation.     

微乳液合成胶体CuO/γ-Al2O3及其催化芳香硝基化合物还原（英文）

Monodispersed colloidal copper oxide nanoparticles were synthesized by water-in-oil microemulsion using CuCl 2·H2O and NaOH.The effect on CuO particle size was studied by varying the water-to-surfactant molar ratio,precursor concentration and molar ratio of NaOH to CuCl2.The morphology,size and size distribution of the particles were studied by transmission electron microscopy and dynamic light scattering.Dispersion destabilization of the colloidal copper oxide nanoparticles was detected by a Turbiscan apparatus.CuO/γ-Al2O3 catalysts were prepared by dispersing highly stable CuO nanoparticles on γ-alumina by mechanical stirring.The catalysts were analyzed by scanning electron microscopy,transmission electron microscopy,X-ray photoelectron,and X-ray diffraction,which confirmed the uniform dispersion of CuO on the support.The reduction of the nitro aromatic compounds,4-nitrophenol,3-nitrophenol,and 2-nitrophenol,were studied.The CuO/γ-Al2O3 catalysts were active for the reduction of these nitro aromatic compounds.     

Characteristics of La-modified Ni-Al2O3 and Ni-SiO2 catalysts for COx-free hydrogen production by catalytic decomposition of methane

Hydrotalcite precursors of La modified Ni-Al2O3 and Ni-SiO2 catalysts prepared by co-precipitation method and the catalytic activities were examined for the production of COx-free H2 by CH4 decomposition. Physico-chemical characteristics of fresh, reduced and used catalysts were evaluated by XRD, TPR and O2 pulse chemisorptions, TEM and BET-SA techniques. XRD studies showed phases due to hydrotalcite-like precursors in oven dried form produced dispersed NiO species upon calcination in static air above 450 C. Raman spectra of deactivated samples revealed the presence of both ordered and disordered forms of carbon. Ni-La-Al2O3catalyst with a mole ratio of Ni : La : Al = 2 : 0.1 : 0.9 exhibited tremendously high longevity with a hydrogen production rate of 1300 molH2 mol 1 Ni. A direct relationship between Ni metal surface area and hydrogen yields was established.     

Methanation of carbon dioxide on Ni/ZrO2-Al2O3 catalysts:Effects of ZrO2 promoter and preparation method of novel ZrO2-Al2O3 carrier

The novel nickel-based catalysts with a nickel content of 12 wt% were prepared with the zirconia-alumina composite as the supports. The new carriers, ZrO2 improved alumina, were synthesized by three methods, i.e., impregnation-precipitation, co-precipitation, and impregnation method. The catalytic properties of these catalysts were investigated in the methanation of carbon dioxide, and the samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscope (XPS), temperature-programmed reduction (TPR) and temperature-programmed desorption (TPD) techniques. The new catalysts showed higher catalytic activity and better stability than Ni/γ-Al2O3. Furthermore, as a support for new nickel catalyst, the ZrO2-Al2O3 composite prepared by the impregnation-precipitation method was more efficient than the other supports in the methanation of carbon dioxide. The highly dispersed zirconium oxide on the surface of γ-Al2O3 inhibited the formation of nickel aluminate-like phase, which was responsible for the better dispersion of Ni species and easier reduction of NiO species, leading to the enhanced catalytic performance of corresponding catalyst.     

CeO2-ZrO2-La2O3-Al2O3 composite oxide and its supported palladium catalyst for the treatment of exhaust of natural gas engined vehicles

Composite supports CeO2-ZrO2-Al2O3 (CZA) and CeO2-ZrO2-Al2O3-La2O3 (CZALa) were prepared by co-precipitation method. Palladium catalysts were prepared by impregnation and their purification ability for CH4, CO and NOx in the mixture gas simulated the exhaust from natural gas vehicles (NGVs) operated under stoichiometric condition was investigated. The effect of La2O3 on the physicochemical properties of supports and catalysts was characterized by various techniques. The characterizations with X-ray diffraction (XRD) and Raman spectroscopy revealed that the doping of La2O3 restrained effectively the sintering of crystallite particles, maintained the crystallite particles in nanoscale and stabilized the crystal phase after calcination at 1000 ℃. The results of N2-adsorption, H2-temperature-programmed reduction (H2-TPR) and oxygen storage capacity (OSC) measurements indicated that La2O3 improved the textural properties, reducibility and OSC of composite supports. Catalytic activity testing results showed that the catalysts exhibit excellent activities for the simultaneous removal of methane, CO and NOx in the simulated exhaust gas. The catalysts supported on CZALa showed remarkable thermal stability and catalytic activity for the three pollutants, especially for NOx. The prepared palladium catalysts have high ability to remove NOx, CH4 and CO, and they can be used as excellent catalysts for the purification of exhaust from NGVs operated under stoichiometric condition. They also have significant potential in industrial application because of their high performance and low cost.     

Study of The Pd-B/ γ-Al2O3 Amorphous Alloy Catalyst

The Pd-B/γ-Al2O3 amorphous alloy catalyst and Pd/γ-Al2O3 crystalline metal catalyst were prepared by KBH4 reduction and routine impregnation,respectively.Pd-B/γ-Al2O3 and Pd/γ-Al2O3 catalysts were characterized by XRD and SEM.It was found that the catalytic activity of the Pd-B/γ-Al2O3 amorphous alloy catalyst was higher than that of the Pd/γ-Al2O3 crystalline metal catalyst in the anthraquinone hydrogenation.     

Preparation of Highly Active Pt-K/γ-Al2O3 Catalyst for o-Phenylphenol Synthesis from o-Cyclohexenyl-cyclohexanone Dehydrogenation

0.5%Pt-K/γ-Al2O3 catalysts for the synthesis of o-phenylphenol（OPP） from o-cyclohexenyl-cyclohexanone （dimer） dehydrogenation were prepared by means of a two subsequent impregnation method. The effects of catalyst preparation parameters, such as K promoters, calcination, and reduction conditions, were investigated. The results showed that the addition of K2SO4 to Pt/γ-Al2O3 catalyst notably promoted the selectivity of OPP, and its optimum content was found to be 6% in mass fraction. The higher activity was obtained when Pt/γ-Al2O3 catalyst was calcined in nitrogen atmosphere at 400--500 ℃ and then reduced at the same temperature for 3 h in hydrogen atmosphere. The conversion of the dimer and the selectivity of OPP were always above 99% and 90%, respectively, over 0.5%Pt-6% K2SO4/γ-Al2O3 catalyst during the pilot scale test of 8000 h.     

Catalytic Combustion of Methane over CO1-xMgxO/Al2O3/FeCrAl Monolithic Catalysts

A series of CoxMgxO/Al2O3/FeCrAl catalysts （x=0-1） were prepared. The structures of the catalysts were characterized using XRD, SEM, and TPR analyses. The catalytic activity of the catalysts for methane combustion was evaluated in a continuous flow microreactor. The results indicated that the active washcoats adhered well on the FeCrAl foils. The phases in the catalysts were Co--xMgxO solid solutions, α-Al2O3, and γ-Al2O3. The surface particle size of the catalysts varied with variations in the molar ratios of Co to Mg. The Co component of the Co1_xMgxO/Al2O3/FeCrAl catalysts played an important role in the catalytic activity for methane combustion. In the Co1-xMgxO/AluO3/FeCrAl series catalyst （x=0.2-0.8）, the catalytic activity in terms of x was in the order of 0.5〉0.2〉0.8 under the experimental conditions. The presence of Mg in these catalysts could promote the thermal stability to a large extent. There were strong interactions between the Co1-xMgxO oxides and the AluO3/FeCrAl supports.     

镍钼杂多酸制备NiMo/γ-Al2O3催化剂及硼、钴或镍改性氧化铝的影响（英文）

A hydrotreating NiMo/γ-Al2O3 catalyst(12 wt% Mo and 1.1 wt% Ni) was prepared by impregnation of the support with the Anderson-type heteropolyoxomolybdate(NH4)4Ni(OH)6Mo6O18.Before impregnation of the support,it was modified with an aqueous solution of H3BO3,Co(NO3)2,or Ni(NO3)2.The catalysts were investigated using N2 adsorption,O2 chemisorption,X-ray diffraction,UV-Vis spectroscopy,Fourier transform infrared spectroscopy,temperature-programmed reduction,temperature-programmed desorption,and X-ray photoelectron spectroscopy.The addition of Co,Ni,or B influenced the Al2O3 phase composition and gave increased catalytic activity for 1-benzothiophene hydrodesulfurization(HDS).X-ray photoelectron spectroscopy confirmed that the prior loading of Ni,Co or B increased the degree of sulfidation of the NiMo/γ-Al2O3 catalysts.The highest HDS activity was observed with the NiMo/γ-Al2O3 catalyst with prior loaded Ni.     

Study of CO2 Hydrogenation to Methanol over Cu-V/γ-Al2O3 Catalyst

The effect of vanadium addition to CU/γ-Al2O3 catalyst used in the hydrogenation of CO2 to produce methanol was studied. It was found that the catalytic performance of the Cu-based catalyst improved after V addition. The influence of reaction temperature, space velocity and the molar ratio of H2 to CO2 on the performance of 12%Cu-6%V/γ-Al2O3 catalyst were also studied. The results indicated that the best conditions for reaction were as follows: 240℃, 3600 h-1 and a molar ratio of H2 to CO2 of 3:1. The results of XRD and TPR characterization demonstrated that the addition of V enhanced the dispersion of the supported CuO species, which resulted in the enhanced catalytic performance of CU-V/γ-Al2O3 binary catalyst.     

Effect of alcohol solvents treated ZrO（OH）2 hydrogel on properties of ZrO2 and its catalytic performance in isosynthesis

A series of ZrO2 catalysts were prepared by treating ZrO(OH)2 hydrogel with different alcohol solvents (C2-C4 alcohols) and calcining under N2 flow at 773 K for 3 h. The obtained ZrO2 catalysts were systematically characterized by the methods of N2 adsorption-desorption, powder X-ray diffraction, NH3 temperature-programmed desorption, and CO2 temperature-programmed desorption. The catalytic performance of each catalyst was evaluated in the selective synthesis of iso-C4 (isobutene and isobutane) and light olefins (C2= ～C4= ) from CO hydrogenation. The specific surface area increased for the ZrO2 catalysts obtained by treating ZrO(OH)2 hydrogel with different alcohol solvents. The amounts of both acidic and basic sites on the catalyst surface increased obviously. The catalytic activity (CO conversion) of ZrO2 catalysts also increased after the treatment with different alcohol solvents. The highest activity was obtained over the catalyst which was pretreated with isopropanol. However, alcohol solvent treatment retarded the transformation of ZrO2 crystal structure from tetragonal phase to monoclinic phase, and subsequently resulted in the decrease of monoclinic phase in ZrO2, which led to the decrease of olefin selectivity in corresponding hydrocarbon products (C2=～C4= /CH).     

Autothermal reforming of methane over Ni catalysts supported over ZrO2-CeO2-Al2O3

Ni catalysts supported on Al2O3, ZrO2-Al2O3, CeO2-Al2O3 and ZrO2-CeO2-Al2O3 were prepared by coprecipitation method, and their catalytic performances for autothermal reforming of methane to hydrogen were investigated. The Ni-supported catalysts were characterized by XRD, TPR and XPS. The relationship between the structures and catalytic activities of the catalysts was discussed. The results showed that the catalytic activity and stability of the Ni/ZrO2-CeO2-Al2O3 catalyst was better than those of other catalysts with the highest CH4 conversion, H2/CO and H2/COx ratio at 750 ℃. The catalyst showed a little deactivation along the reaction time during its 72 h on stream with the mean deactivation rate of 0.08%/h. The catalytic performance of the Ni/ZrO2-CeO2-Al2O3 catalyst was also affected by reaction temperature, no2 ： nCH4 molar ratio and nH2O ： nCH4 molar ratio. TPR, XRD and XPS measurements indicated that the formation of ZrO2-CeO2 solid solution could improve the dispersion of NiO, and inhibit the formation of NiAl2O3, and thus significantly promoted the catalytic activity of the Ni/ZrO2-CeO2-Al2O3 catalyst.     

Role of support nature （γ-Al2O3 and SiO2-Al2O3） on the performances of rhenium oxide catalysts in the metathesis of ethylene and 2-pentene

The metathesis of ethylene and 2-pentene was studied as an alternative route for propylene production over Re2O7/γ-Al2O3 and Re2O7/SiO2-Al2O3 catalysts. Both NH3 temperature-programmed desorption (NH3-TPD) and H2 temperature-programmed reduction (H2-TPR) results showed that Re2O7/SiO2-Al2O3 exhibited stronger acidity and weaker metal-support interaction than Re2O7/γ-Al2O3. At 35 60℃, isomerization free metathesis was observed only over Re2O7/γ-Al2O3, suggesting that the formation of metal-carbene metathesis active sites required only weak acidity. Our results suggest that on the Re2O7/SiO2-Al2O3, hydrido-rhenium species ([Re]-H) were formed in addition to the metathesis active sites, resulting in the isomerization of the initial 1-butene product into 2-butenes. A subsequent secondary metathesis reaction between these 2-butenes and the excess ethylene could explain the enhanced yields of propylene observed. The results demonstrate the potential for high yield of propylene from alternative feedstocks.     

Efficient oxidative degradation of 2-chlorophenol and 4-chlorophenol over supported CuO-based catalysts

A series of metal oxide catalysts for catalytic oxidative degradation of 2-chlorophenol (2-CP) and 4-chlorophenol (4-CP) were prepared, and the supported CuO catalysts were studied particularly. The supported CuO catalysts were characterized by XRD and NH3-TPD techniques, in which CuO/γ-Al2O3 exhibited high degradation activity. The addition of Na2O or K2O into CuO/γ-Al2O3 improved the oxidative degradation of CPs remarkably, in which Na2O was more efficient than K2O. Over CuO/γ-Al2O3-Na2O, CPs were completely converted and the liberation of the inorganic chloride from 2-CP or 4-CP reached 97% or 100% respectively at 30 ?C for 2 h. The supported CuO catalysts with good dispersion of CuO particles and less acid sites were favorable for the efficient oxidative degradation of CPs. In addition, the initial pH of the reaction solution was found to be an important factor which influenced the catalytic oxidative degradation of CPs and the initial pH of 11.2 and 9.8 was preferred for the oxidative degradation of 2-CP and 4-CP respectively over CuO/γ-Al2O3 catalyst.     

Al2O3负载Cu,Fe或Ni掺杂氧化钼催化乙苯氧化脱氢（英文）

Molybdenum-based catalysts supported on Al2O3 doped with Ni, Cu, or Fe oxide were synthesized and used in ethylbenzene dehydrogenation to produce styrene. The molybdenum oxide was sup-ported using an unconventional route that combined the polymeric precursor method (Pechini) and wet impregnation on commercial alumina. The samples were characterized by X-ray diffraction (XRD), N2 adsorption-desorption isotherms, temperature-programmed reduction of H2 (H2-TPR), and thermogravimetric (TG) analysis. XRD results showed that the added metals were well dis-persed on the alumina support. The addition of the metal oxide (Ni, Cu, or Fe) of 2 wt% by wet im-pregnation did not affect the texture of the support. TPR results indicated a synergistic effect be-tween the dopant and molybdenum oxide. The catalytic tests showed ethylbenzene conversion of 28%–53% and styrene selectivity of 94%–97%, indicating that the addition of the dopant improved the catalytic performance, which was related to the redox mechanism. Molybdenum oxides play a fundamental role in the oxidative dehydrogenation of ethylbenzene to styrene by its redox and acid–base properties. The sample containing Cu showed an atypical result with increasing conver-sion during the reaction, which was due to metal reduction. The Ni-containing solid exhibited the highest amount of carbon deposited, shown by TG analysis after the catalytic test, which explained its lower catalytic stability and selectivity.     

Investigation of CO and formaldehyde oxidation over mesoporous Ag/Co3O4 catalysts

CO and formaldehyde(HCHO)oxidation reactions were investigated over mesoporous Ag/Co3O4 catalysts prepared by one-pot(OP)and impregnation(IM)methods.It was found that the one-pot method was superior to the impregnation method for synthesizing Ag/Co3O4 catalysts with high activity for both reactions.It was also found that the catalytic behavior of mesoporous Co3O4 and Ag/Co3O4 catalysts for the both reactions was different.And the addition of silver on mesoporous Co3O4 did not always enhance the catalytic activity of final catalyst for CO oxidation at room temperature(20 C),but could significantly improve the catalytic activity of final catalyst for HCHO oxidation at low temperature(90 C).The high surface area,uniform pore structure and the pretty good dispersion degree of the silver particle should be responsible for the excellent low-temperature CO oxidation activity.However,for HCHO oxidation,the addition of silver played an important role in the activity enhancement.And the silver particle size and the reducibility of Co3O4 should be indispensable for the high activity of HCHO oxidation at low temperature.