Baeyer–Villiger oxidation of cyclohexanone catalyzed by cordierite honeycomb washcoated with Mg–Sn–W composite oxides

In this work, a series of Mg–Sn–W oxide powder catalysts with different tungsten oxide contents(0, 15 wt% and 30 wt%) were prepared and washcoated on cordierite honeycomb monoliths to produce monolithic catalysts,which were tested for the Baeyer–Villiger oxidation of cyclohexanone. The obtained monolithic catalysts,which combined the advantages of both homogeneous and heterogeneous catalysts, showed high catalytic efficiency and overcame the problems of product separation that occurred in the homogeneous catalytic process.SEM and EDX tests showed that the catalytic coating, with a thickness of approximately 20 μm, was compact and homogeneous, and an enlarged BET surface area was indicated by N_2 adsorption–desorption compared with the bare cordierite honeycomb. The chemical properties on the catalytic surface of the powder and monolithic catalysts were characterized by XPS, which indicated the tin and tungsten on the catalysts exhibited their full oxide states and presented mainly as stannate and tungstate, as confirmed by XRD and FTIR characterizations.Moreover, the catalytic activity test indicated that the tungsten content of the catalysts played an important role in catalytic efficiency and that monolithic catalysts were produced without obvious catalytic activity loss compared with the corresponding powders.(M)W30, which exhibited excellent mechanical stability and maintained high activity after recycling three times, was the optimal catalyst, showing a high selectivity that exceeded 86%and a conversion above 64%. Therefore, the structured Mg–Sn–W oxide catalysts have great potential for application in practical production.     

焙烧温度对加氢脱氮催化剂性能的影响

A series of Mo/Ni-based hydrotreating catalysts calcined at different temperatures was prepared by impregnation method,and characterized by means of N₂ adsorption-desorption,NH₃-TPD and TPR techniques.The HDN performance of the catalysts was investigated in a microreactor.The results indicated that with the increase of calcination temperatures,the specific surface area of the catalysts was decreased,the average pore size was gradually increased,and the pore volume change was very small.The acid amount on the surface of the catalysts showed a tendency to ascend firstly, and then to descend with the increase of calcination temperatures, and the acid amount reached the maximum at 500 ℃. The activity of the hydrotreating catalysts was enhanced firstly and then reduced with the increase of calicination temperature,and the optimal calcination temperature was 500 ℃.On the whole,the activity of the catalysts could be improved prepared under suitable calcination temperature,and be suppressed obtained under high calcination temperature.     

Performance of Ni/Nano-ZrO2catalysts for CO preferential methanation简

Large surface areas nano-scale zirconia was prepared by the self-assembly route and was employed as support in nickel catalysts for the CO selective methanation. The effects of Ni loading and the catalyst calcination temperature on the performance of the catalyst for CO selective methanation reaction were investigated. The cata- lysts were characterized by Brunauer-Emmett-Teller （BET）, transmission electron microscope （TEM）, X-ray dif- fraction （XRD） and temperature-programmed reduction （TPR）. The results showed that the as-synthesized Ni/nano-ZrO2 catalysts presented high activity for CO methanation due to the interaction between Ni active particle and nano zir- conia support. The selectivity for the CO methanation influenced significantly by the particle size of the active Ni species. The exorbitant calcination resulted in the conglomeration of dispersive Ni particles and led to the decrease of CO methanation selectivity. Among the catalysts studied, the 7.5% （by mass） Ni/ZrO2 catalyst calcinated at 500℃ was the most effective for the CO selective methanation. It can preferentially catalyze the CO methanation with a higher 99% conversion in the CO/CO2 competitive methanation system over the temperature range of 260-280℃, while keeping the CO2 conversion relatively low.     

Synthesis and catalytic activity of SBA-15 supported catalysts for styrene oxidation

Cu(II) and Mn(II) metals embedded on mesoporous SBA-15 were synthesized by co-precipitation technique.The support and catalysts were characterized by SEM–EDX,TEM,BET,XRD and ICP-AES methods.The catalytic activity of these catalysts was evaluated for styrene oxidation at various reaction conditions such as styrene to TBHP mole ratio,temperature,catalyst amount by using TBHP as an oxidizing agent.Major reaction products were styrene oxide and benzaldehyde and highest styrene conversion(97.3%) was observed at styrene to TBHP mole ratio of 1:4,temperature at 80 °C and 20 mg of catalyst.Further,the recyclability of the catalysts was observed and found that they can be recycled three times without major loss in their activity and selectivity.     

金属卟啉催化的甲苯氧化及工艺优化

Catalytic activities of a series of metalloporphyrin complexes in selective aerobic oxidation of toluene were investigated.The effects of different central metal ions in metalloporphyrins[T（p-Cl）PPMCl（M=Fe,Co,Mn,Cu）] on the reaction course had been examined and it was found that T（p-Cl）PPCu presented the highest catalytic activity in the reaction.The reaction conditions of toluene oxidation were optimized by using orthogonal experiment design.Five relevant factors were investigated：temperature,air pressure,catalyst loading,air flow rate and reaction time.The effects of the five factors on both toluene conversion and total yield of benzaldehyde and benzyl alcohol were discussed.The research results showed that the reaction temperature was the most significant factor influencing toluene oxidation.On the basis of the margin analysis,the optimum conditions for the toluene conversion and the total yield of benzaldehyde and benzyl alcohol respectively were achieved,under which the toluene conversion was up to 14.67%and the total yield of benzaldehyde and benzyl alcohol reached 5.89%.     

邻氯苯酚废水的催化湿式氧化处理

Catalytic wet air oxidation (CWAO) was investigated in laboratory-scale experiments for the treatment of o-chlorophenol in wastewater. Experimental results showed that wet air oxidation (WAO) process in the absence of catalyst was also effective for o-chlorophenol in wastewater treatment. Up to 80% of the initial CODCr was removed by wet air oxidation at 270℃ with twice amount of the required stoichiometric oxygen supply. At temperature of 150℃, the removal rate of CODCr was only 30%. Fe2(SO4)3, CuSO4, Cu(NO3)2 and MnSO4 exhibited high catalytic activity. Higher removal rate of CODCr was obtained by CWAO. More than 96% of the initial CODCr was removed at 270℃ and 84.6%-93.6% of the initial CODCr was removed at 150℃. Mixed catalysts had better catalytic activity for the degradation of o-chlorophenol in wastewater.     

KF/MgO催化酯交换法合成碳酸二月桂酯

The catalytic properties of KF/MgO for the synthesis of didodecyl carbonate (DDC) by transesterification from dimethyl carbonate (DMC) and dodecanol were studied. The effects of loading amount of KF and calcining temperature were systemically investigated. The phase structure was characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Interaction between KF and the carrier MgO occurred in the process of calcination, and a new phase K2MgF4 formed when calcining temperature was 673 K or above. FTIR results showed that K2CO3 was observed when catalysts calcined in air. When calcining tem-perature was 873 K and the loading mass amount of KF was 30%, the KF/MgO catalyst exhibited the optimal catalytic properties and the yield of DDC was maximized to 80%. The excellent catalytic properties of KF/MgO was ascribed to the formation of K2MgF4+K2CO3 during the calcination in air.     

Catalytic Wet Air Oxidation of oChlorophenol in Wastewater

Catalytic wet air oxidation (CWAO) was investigated in laboratory-scale experiments for the treatment of o-chlorophenol in wastewater. Experimental results showed that wet air oxidation (WAO) process in the absence of catalyst was also effective for o-chlorophenol in wastewater treatment. Up to 80% of the initial CODcr was removed by wet air oxidation at 270℃ with twice amount of the required stoichiometric oxygen supply. At temperature of 150℃, the removal rate of CODCr was only 30%. Fe2(SO4)3, CuSO4, Cu(NO3)2 and MnSO4 exhibited high catalytic activity. Higher removal rate of CODcr was obtained by CWAO. More than 96% of the initial CODcr was removed at 270℃ and 84.6%-93.6% of the initial COD Cr was removed at 150℃. Mixed catalysts had better catalytic activity for the degradation of o-chlorophenol in wastewater.     

燃烧法制备二氧化钛催化剂的条件对其可见光催化性能的影响

Titania catalysts were synthesized by a solution combustion method （SCM）. Photodegradation of 4-chlorophenol （4-CP） using the synthesized catalysts was studied under both visible light （λ≥420nm） and sunlight irradiation. The effect of preparation conditions on photocatalytic activities of the synthesized catalysts was investigated. The optimal photocatalytic activity of the catalyst （denoted as A1 ） was obtained under the following synthesis conditions： ignition temperature of 350~C, fuel ratio （ φ） of 1 and calcination time of lh. The degradation and mineralization ratio of 4-CP were 78.2% and 53.7% respectively under visible light irradiation for 3h using catalyst A1. And the catalyst A1 also showed high photocatalytic activity under sunlight irradiation.     

载体二氧化钛的晶型对对硝基苯酚加氢催化剂Ni/TiO2的影响

The catalytic hydrogenation ofp-nitrophenol to p-aminophenol was investigated over Ni/TiO2 catalysts prepared by a liquid-phase chemical reduction method. The catalysts were characterized by inductively coupled plasma （ICP）, X-ray powder diffraction （XRD）, transmission electron microscopy （TEM）, X-ray photoelectron spectra （XPS） and temperature-programmed reduction （TPR）. Results show that the titania structure has favorable influence on physio-chemical and catalytic properties of Ni/TiO2 catalysts. Compared to commercial Raney nickel, the catalytic activity of Ni/TiO2 catalyst is much superior, irrespective of the titania structure. The catalytic activity of anatase titania supported nickel catalyst Ni/TiO2（A） is higher than that of rutile titania supported nickel catalyst Ni/TiO2（R）, possibly because the reduction of nickel oxide to metallic nickel for Ni/TiO2（A） is easier than that for Ni/TiO2（R） at similar reaction conditions.     

W-HMS催化剂的原位法制备研究

以钨酸为原料,通过原位合成法将W~(6+)引入六方介孔全硅分子筛HMS骨架中,制备了W- HMS催化剂。采用XRD、FT-IR以及EDS对所得催化剂结构进行了表征,并通过环戊烯过氧化氢非均相催化氧化制备戊二醛,考察了其催化活性。结果显示,W-HMS催化剂的催化性能与W的量密切相关．在n_(si)/n_w(物质的量比)大于或等于30时,催化剂保持了完好的HMS分子筛结构,W原子以嵌入HMS骨架的形式高度分散于载体内表面,构成催化活性中心,对环戊烯氧化反应转化率可达100%,生成戊二醛的选择性达79．3%。     

Synergy between tungsten and palladium supported on titania for the catalytic total oxidation of propane

Titania-supported palladium catalysts modified by tungsten have been tested for the total oxidation of propane. The addition of tungsten significantly enhanced the catalytic activity. Highly active catalysts were prepared containing a low loading of 0.5 wt.% palladium, and activity increased as the tungsten loading was increased up to 6 wt.%. Catalysts were characterised using a variety of techniques, including powder X-ray diffraction, laser Raman spectroscopy, X-ray photoelectron spectroscopy, temperature-programmed reduction and aberration-corrected scanning transmission electron microscopy. Highly dispersed palladium nanoparticles were present on the catalyst with and without the addition of WO_x. However, the addition of WO_x slightly increases the average palladium particle size, and there was some evidence for the Pd forming epitaxial islands on the support in the tungsten-doped samples. Surface analysis identified a combination of Pd⁰ and Pd²⁺ on a Pd/TiO₂ catalyst, whereas all of the Pd loading was found in the form of Pd²⁺ with the addition of tungsten into the catalysts. At low tungsten loadings, isolated monotungstate and some polytungstate species were highly dispersed over the titania support. The concentration of polytungstate species increased as the loading was increased, and it was also promoted by the presence of palladium. The coverage of the highly dispersed tungstate species over the titania also increased as the tungsten loading increased. Some tungstate species were also found to be associated with the palladium oxide particles, and there was an enrichment of oxidised tungsten species at the peripheral interface of the palladium oxide nanoparticles and the titania. Sub-ambient temperature–programmed reduction experiments identified an increased concentration of highly reactive species on catalysts with palladium and tungsten present together, and we propose that the new WO_x-decorated interface between PdO_x and TiO₂ particles may be responsible for the enhanced catalytic activity in the co-impregnated catalysts.     

An effective heterogeneous WO3/TiO2–SiO2 catalyst for selective oxidation of cyclopentene to glutaraldehyde by H2O2

TiO₂–SiO₂ mixed oxide with large pore size was synthesized by the xerogel method and it was then used to prepare the WO₃/TiO₂–SiO₂ catalyst by an incipient wetness method. The as‐prepared WO₃/TiO₂–SiO₂ sample was employed as the first heterogeneous catalyst in the liquid‐phase cyclopentene oxidation by aqueous H₂O₂, which exhibited higher selectivity (about 75%) to glutaraldehyde (GA) and, in turn, higher GA yield than the WO₃/SiO₂ heterogeneous catalyst and even the tungstic acid homogeneous catalyst under the same reaction conditions. The amorphous WO₃ phase was identified as the active sites and the loss of the active sites was proved to be not important. The lifetime of the catalyst was determined and its regeneration method was proposed. The effects of various factors on the catalytic behaviors, such as the WO₃ loading, the calcination temperature, the surface acidity and the reaction media, were investigated and discussed based on various characterizations including BET, XRD, XPS, FTIR, EXAFS and Raman spectra etc. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis and characterization of W-SBA-15 and W-HMS as supports for HDS

W-modified HMS and SBA-15 mesoporous materials (Si/W molar ratio equal to 40) were synthesized using sodium tungstate as tungsten source. In order to prepare NiW catalysts these mesoporous materials were impregnated with an aqueous solution of nickel salt of 12-tungstophosphoric acid Ni_3/2PW₁₂O₄₀. The synthesized W-HMS, W-SBA-15 materials and NiW catalysts have been characterized by S_BET, XRD, UV–Vis DRS, FT-IR, TPD of NH₃, ²⁹Si MAS NMR, SEM and HRTEM. The influence of these particular supports on catalytic activity of NiW catalysts was studied in the reaction of hydrodesulfurization (HDS) of thiophene. The results from the FT-IR and UV–Vis DR spectroscopy confirm incorporation of W into the HMS and SBA-15 structures. Additionally ²⁹Si MAS NMR measurements revealed relatively stronger effect of W ion incorporation in HMS structure on degree of silica cross-linking as compared to the effect of W ion incorporation in SBA-15 structure. The catalytic study showed that both W-HMS and W-SBA-15 materials modified with W are good supports for NiW catalysts in the HDS reaction of thiophene. The catalysts show lower selectivity for butanes than a reference NiW/γ-Al₂O₃ catalyst leveling of about 10% for chosen experimental conditions.     

The role of the WO x ad-component to Pt and PtRu catalysts in the electrochemical CH3OH oxidation reaction

High surface area carbon-supported platinum-based catalysts, Pt/C, PtWO _x /C, PtRu/C and PtRuWO _x /C, were prepared via a chemical reduction route using single metal precursor salts. The catalyst particles were found to be in the nanoscale range, and the addition of Ru clearly decreased the particle size. The Ru was found to be partially incorporated into the face centered cubic lattice of Pt and to form a single Ru catalyst component. X-ray diffraction and X-ray photon spectroscopy did not provide evidence for electronic interactions between WO _x and Pt as well as WO _x and Ru. However, the addition of tungsten to the PtRuWO _x /C catalyst resulted in a high degree of catalyst particle agglomeration. Both Ru containing catalysts showed significantly higher activities for the CH₃OH oxidation reaction in terms of Pt + Ru mass as well as electroactive Pt + Ru surface area than the Pt/C and PtWO _x /C catalysts. The addition of tungsten appeared to mainly result in some ‘physical’ modification of the catalytically active Pt and Ru surface components such as differences in electroactive surface area rather than promotion of the CH₃OH oxidation reaction via a true catalytic mechanism.     

Novel Heterogeneous W-Doped MCM-41 Catalyst for Highly Selective Oxidation of Cyclopentene to Glutaraldehyde by Aqueous H2O2

W-doped MCM-41 (W-MCM-41) has been reported as a novel heterogeneous catalyst for the selective oxidation of cyclopentene to prepare glutaraldehyde with environmentally benign aqueous hydrogen peroxide. It is found that tungsten species could stably exist in the silica-based matrix of MCM-41 up to a Si/W molar ratio of 40 by means of X-ray diffraction, laser Raman spectroscopy, scanning electron microscopy, etc. Proper content of tungsten species, high specific surface area and large mean pore size of the W-MCM-41 account mainly for its high catalytic activity in comparison with other W-containing heterogeneous catalysts. Complete conversion of cyclopentene and very high yield of glutaraldehyde (72%) are obtained over the W-MCM-41 catalyst with an Si/W molar ratio of 40. Furthermore, almost no tungsten species are leached into the reaction solution, enabling the catalyst to be employed for many reaction cycles without obvious degeneration. The correlation of the catalytic behavior with the special structural characteristics of the W-MCM-41 catalyst is also discussed through various characterization methods.     

Novel efficient and green approach to the synthesis of glutaraldehyde over highly active W-doped SBA-15 catalyst

In the present work, we demonstrate for the first time the use of W-doped SBA-15 catalyst prepared by a novel in situ synthesis method as highly efficient catalyst for the direct production of glutaraldehyde via selective oxidation of cyclopentene by using non-aqueous hydrogen peroxide as the green oxidant. It is suggested that the presence of a high surface concentraiton of WO_x species dispersed on well ordered hexagonal pore walls of SBA-15 support is essential to the superior performance of the catalyst for the selective oxidation of cyclopentene.     

Effect of acid type in WO X clusters on the esterification of ethanol with acetic acid

Tungsten oxide clusters supported on silica (WO _X /SiO₂) with different W loading levels and the effect of acid type on the esterification of acetic acid with ethanol were examined. The catalysts were characterized using various techniques (XRD, Raman spectroscopy, NH₃-TPD and FT-IR) to investigate the crystallinity and the nature of the acid sites. The change in the composition of two tungsten oxide species (polytungstate and crystalline WO₃) leads to the change of Lewis acid to Br?nsted acid ratio. Importantly, the ratio of the two different acid types has a substantial effect on the catalytic activity. The fraction of Lewis acid to total acid sites rapidly changed from 23% to 77% due to the presence of crystalline WO₃. Where the Lewis acid sites accounted for 55% of the total acid sites, the WO _X /SiO₂ catalyst showed the highest catalytic activity among the prepared catalysts.     

Oxidation of cyclopentene catalyzed by tungsten-substituted molybdophosphoric acids

A series of Keggin type tungsten-substituted molybdophosphoric acids (H₃PMo_12−n W _n O₄₀·XH₂O) were synthesized and characterized by ICP-AES, FT-IR, TG-DSC, and XRD. The tungsten substitution extent significantly affected their catalytic activity in the oxidation of cyclopentene and the selectivity of the resultant products. The tungsten-substituted molybdophosphoric acids with tungsten substitution numbers in a range of 3–6.8 exhibited high catalytic activity in the oxidation of cyclopentene. After reaction for 8 h, the conversion of cyclopentene was up to 97%; the oxidation products mainly consisted of glutaraldehyde, cis-1,2-cyclopentanediol and trans-1,2-cyclopentanediol with the yields of ca. 23%, 27%, and 45%, respectively.     

WO_3/HMS催化剂多相催化氧化环戊烯合成戊二醛

以(NH4)2WO4为钨源制备的WO3/HMS分子筛为催化剂,过氧化氢为氧化剂,考察了在环戊烯氧化制备戊二醛的多相催化反应中反应时间、反应温度、催化剂质量、溶剂用量和氧化剂质量分数等因素对戊二醛收率的影响。筛选出WO3/HMS催化环戊烯(CPE)合成戊二醛反应的适宜工艺条件:n(H2O2)∶n(W)∶n(CPE)=2∶0.025∶1,V(t-BuOH)∶V(CPE)=8∶1,反应温度为35℃,反应时间为30 h。戊二醛的收率可达67%。