使用分子氧催化氧化法合成肉桂醛的研究

肉桂醛主要用于食品、药品及化妆品的香料，调味品及甜酒等的肉桂香型调味剂。传统的工业生产方法主要有：由桂皮油、肉桂油等天然油与亚硫酸氢钠的加成法；由苯甲醛与乙醛先在碱性条件下发生羟醛缩合反应再用苯进行溶剂抽提的生产方法。近年来，在从农、副林业产品生产以乙醇为主的多种醇类作为重要的化工原料方面已经显现出了广阔的前景。国外化学化工领域中由醇类经催化氧化生产羰基化合物已成为最近几年来的一个热门研究领域。这里报道使用分子氧(源于空气中的氧)催化氧化肉桂醇合成肉桂醛的研究。

复合催氧化法处理生物难降解性有机废水

对于一些染料及其中间体生产过程中产生的废水，直接采用生化法处理往往较困难，采用化学氧化法处理效果较理想，臭氧氧化即是其中的一种，为了提高臭氧的氧化效果，降低处理成本，本研究采用某些金属氧化物、金属盐、Ｈ２Ｏ２、ＮａＣｌＯ与Ｏ３组成复合催化氧化体系，对难生物降解的水溶性染料，进行了处理研究，试验获得了满意的结果。

Ti-ZSM-5骨架钛的表征和催化活性的研究

采用 Ti Cl4二次合成法 ,合成了不同钛含量的 Ti-ZSM-5分子筛 ,用 XRD,UV-Vis,XPS,IR等方法对分子筛进行了表征 ,XRD,XPS及 UV-Vis证明分子筛所载的钛进入分子筛骨架 ,但 IR却出现与文献报道不同的结果 :钛硅分子筛的 IR在 960 cm- 1 处没有吸收峰 ;同时利用该分子筛催化苯乙烯氧化反应 。

Low-temperature catalytic oxidation of formaldehyde over Co_3O_4catalysts prepared using various precipitants

Co3O4 catalysts prepared with different precipitants（NH3·H2O,KOH,NH4HCO3,K2CO3 and KHCO3）were investigated for the oxidation of formaldehyde（HCHO）.Among these,KHCO3-precipitated Co3O4（KHCO3-Co） was the most active low-temperature catalyst,and was able to completely oxidize HCHO at the 100-ppm level to CO2 at 90℃.In situ diffuse reflectance infrared spectroscopy demonstrated that hydroxyl groups on the catalyst surface were regenerated by K~＋ and CO3^（2-）,thus promoting the oxidation of HCHO.Moreover,H2-temperature programmed reduction and X-ray photoelectron spectroscopy showed that employing KHCO3 as the precipitant increased the Co^3＋/Co^2＋molar ratio on the surface of the Co3O4 catalyst,thus further promoting oxidation.Structural characterization revealed that catalysts precipitated with carbonate or bicarbonate reagents exhibited greater specific surface areas and pore volumes.Overall,these data suggest that the high activity observed during the Co3O4 catalyzed oxidation of HCHO can be primarily attributed to the presence of K~＋ and CO3^（2-） on the Co3O4 surface and the favorable Co^3＋/Co^2＋ ratio.

Catalytic wet oxidation of aniline over Ru catalysts supported on a modified TiO_2

The catalytic wet air oxidation of aniline over Ru catalysts supported on modified Ti 2 （Ti 2, Ti0.9Ce0.1O2, Ti0.9Zr0.1O2） is investigated. A series of characterization techniques are conducted to determine the relationship between the physico-chemical properties and the catalytic performance. As a result of the good metal dispersion and large number of surface oxygen species, the Ru/Ti0.9 Zr0.1O2 catalyst presents the best catalytic activity among the tested samples. The effects of the operating conditions on the reaction are investigated and the optimal reaction conditions are determined. Based on the relationship between the by-products concentration and the reaction time, the reaction path for the catalytic oxidation of aniline is established. Carbonaceous deposits on the surface of the support are known to be the main reason for catalyst deactivation. The catalysts maintain a constant activity even after three consecutive cycles.

取代芳环硼酸化合物的合成进展

取代芳环硼酸(酯)的合成方法主要有:有机锂试剂法、格氏试剂法和钯催化氧硼基化法.对上述合成方法及其优缺点和进展进行了综述。

Progress in the Technology for Desulfurization of Crude Oil

The poor quality of crude oil obviously leads to high sulfur contents of oil products, and the technology for desulfurization of crude oil is urgently needed so that the sulfur contents in petroleum product could be reduced from the root. This paper describes the progress in technology for desulfurization of crude oil. The present technologies for desulfurization of crude oil include caustic washing, dry gas desulfurization, hydrodesulfurization （HDS）, etc. The new combined technologies for desulfurization of crude oil being studied are： biodesulfurization （BDS）, hydrogenationbacterial catalysis, the microwave-catalytic hydrogenation, the BDS-OD-RA desulfurization and oxidative desulfurization in electrostatic fields, and the ultrasonic/microwave-catalytic oxidation applied in our lab, with their development trends being also discussed.

Importance, features and uses of metal oxide catalysts in heterogeneous catalysis

This short review paper aims at assembling the present state of the art of the multiuses of metal oxides in heterogeneous catalysis, concerning liquid and gaseous phases of the reactant mixtures on solid catalysts. It includes the description of the main types of metal oxide catalysts, of their various preparation procedures and of the main reactions catalysed by them (acid-base type, selective and total oxidations, bi-functional catalysis, photocatalysis, biomass treatments, environmental catalysis and some of the numerous industrial applications). Challenges and prospectives are also discussed.

Preparation and application of perovskite-type oxides for electrocatalysis in oxygen/air electrodes

Recent advances in the preparation and application of perovskite-type oxides as bifunctional electrocatalysts for oxygen reaction and oxygen evolution reaction in rechargeable metal-air batteries are presented in this review.Various fabrication methods of these oxides are introduced in detail,and their advantages and disadvantages are analyzed.Different preparation methods adopted have great influence on the morphologies and physicochemical properties of perovskite-type oxides.As a bifunctional electrocatalyst,perovskite-type oxides are widely used in rechargeable metal-air batteries.The relationship between the preparation methods and the performances of oxygen/air electrodes are summarized.This work is concentrated on the structural stability,the phase compositions,and catalytic performance of perovskite-type oxides in oxygen/air electrodes.The main problems existing in the practical application of perovskite-type oxides as bifunctional electrocatalysts are pointed out and possible research directions in the future are recommended.

Selective catalytic reduction of NO with NH_3 over sol-gel-derived CuO-CeO_2-MnO_x/γ-Al_2O_3 catalysts

Granular CuO-CeO2-MnOx/γ-Al2O3 catalysts were synthesized by the sol-gel method. The performance of the CuO-CeO2-MnOx/γ-Al2O3 catalysts for the selective catalytic reduction (SCR) was studied in a fixed bed system. Preliminary tests were carried out to analyze the behavior of NH3 and NO over catalyst in the presence of oxygen. The optimum temperature range for SCR over the CuO-CeO2-MnOx/γ-Al2O3 catalysts is 300-400 ℃ . The catalysts maintain nearly 100% NO conversion at 350 ℃. The NH3 oxidation experiments show that both NO and N2O are produced gradually with the increase of temperature. The catalysts in this experiment have a stronger oxidation property on NH3, which improves the denitrification activity at low temperature. The over-oxidation of NH3 at high temperature is the main cause leading to a decrease in the NO conversion. The NH3 and NO desorption experiments show that NH3 and NO can be adsorbed on CuO-CeO2-MnOx/γ-Al2O3 granular catalysts. The transient response of NH3 and NO indicates that the SCR reaction proceeds in accordance with the Eley-Rideal mechanism. The adsorbed NO has little influence on the denitrification activity in SCR process.

Estimation of Kinetic Parameters for Autocatalytic Oxidation of Cyclohexane Based on a Modified Adaptive Genetic Algorithm

A modified genetic algorithm of multiple selection strategies, crossover strategies and adaptive operator is constructed, and it is used to estimate the kinetic parameters in autocatalytic oxidation of cyclohexane. The influences of selection strategy, crossover strategy and mutation strategy on algorithm performance are discussed. This algorithm with a specially designed adaptive operator avoids the problem of local optimum usually associated with using standard genetic algorithm and simplex method. The kinetic parameters obtained from the modified genetic algorithm are credible and the calculation results using these parameters agree well with experimental data. Furthermore, a new kinetic model of cyclohexane autocatalytic oxidation is established and the kinetic parameters are estimated by using the modified genetic algorithm.

Influence of preparation methods on the physicochemical properties and catalytic performance of MnO_x-CeO_2 catalysts for NH_3-SCR at low temperature

This work examines the influence of preparation methods on the physicochemical properties and catalytic performance of MnOx‐CeO2 catalysts for selective catalytic reduction of NO by NH3 (NH3‐SCR) at low temperature. Five different methods, namely, mechanical mixing, impregnation,hydrothermal treatment, co‐precipitation, and a sol‐gel technique, were used to synthesizeMnOx‐CeO2 catalysts. The catalysts were characterized in detail, and an NH3‐SCR model reaction waschosen to evaluate the catalytic performance. The results showed that the preparation methodsaffected the catalytic performance in the order: hydrothermal treatment > sol‐gel > co‐precipitation> impregnation > mechanical mixing. This order correlated with the surface Ce3+ and Mn4+ content,oxygen vacancies and surface adsorbed oxygen species concentration, and the amount of acidic sitesand acidic strength. This trend is related to redox interactions between MnOx and CeO2. The catalystformed by a hydrothermal treatment exhibited excellent physicochemical properties, optimal catalyticperformance, and good H2O resistance in NH3‐SCR reaction. This was attributed to incorporationof Mnn+ into the CeO2 lattice to form a uniform ceria‐based solid solution (containing Mn‐O‐Cestructures). Strengthening of the electronic interactions between MnOx and CeO2, driven by thehigh‐temperature and high‐pressure conditions during the hydrothermal treatment also improved the catalyst characteristics. Thus, the hydrothermal treatment method is an efficient and environment‐friendly route to synthesizing low‐temperature denitrification (deNOx) catalysts.

Acid Separation, Catalytic Oxidation and Coagulation for ATC Waste Liquid Treatment

It is difficult to treat 2-amino-thiazoline-4-carboxylic acid （ATC） waste liquid effectively at present for its characteristics of high chemical oxygen demand （COD）, high salinity and low biodegradability. In order to solve this problem, this paper presents several kinds of physical-chemical treatment unit techniques, including acid separation, catalytic oxidation and coagulation. First of all, acid separation was adopted to precipitate relevant organics at isoelectric point. When the temperature and pH value of acid separation were controlled at about 5 ℃ and 2.2 respectively, the COD removal rate could reach 27.600. Secondly, oxidation was used to break chemical constitution of refractory organics. The optimal reaction parameters of catalytic oxidation should be 20 ℃, pH adjusted to 5.0 and [Fe2+] 300 mg/L. Then with 500 H2O2 added and after one-hour reaction, the COD removal rate could achieve about 5200. Finally, coagulation was adopted to remove a portion of refractory organics, and 1500 polymeric molysite flocculant was the best for the coagulation, and the COD removal rate could reach about 1500. Therefore, the proposed feasible process of physical-chemical pretreatment for ATC waste liquid could have about 7000 COD removed in total.

THE PREPARATION AND PHOTOCATALYTIC ABILITY OF LEAD TITANATE

he perovskite-type PbTiO3 has been synthesized by the method of mixed oxides. The appropriate conditions for preparing have been reported. The obtained PbTiO3 powder is pure and fine. The decolorization of dyes in a PbTiO3 suspension system is over 90%. In this paper the photocatalytic ability of PbTiO3 and the factors of influence are discussed.

Immobilization of metalloporphyrins on CeO_2@SiO_2 with a core-shell structure prepared via microemulsion method for catalytic oxidation of ethylbenzene

Ce O2@Si O2 core-shell nanoparticles were prepared by microemulsion method, and metalloporphyrins were immobilized on the Ce O2@Si O2 core-shell nanoparticles surface via amide bond. The supported metalloporphyrin catalysts were characterized by N2 adsorption-desorption isotherm(BET), scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD), ultraviolet and visible spectroscopy(UV-Vis), and Fourier transform infrared spectroscopy(FT-IR). The results show that the morphology of Ce O2@Si O2 nanoparticles is core-shell microspheres with about 30 nm in diameter, and metalloporphyrins are immobilized on the Ce O2@Si O2 core-shell nanoparticles via amide bond. Especially, the core-shell structure contains multi Ce O2 core and thin Si O2 shell, which may benefit the synergistic effect between the Ce O2 core and the porphyrin anchored on the very thin Si O2 shell. As a result, this supported metalloporphyrin catalysts present comparably high catalytic activity and stability for oxidation of ethylbenzene with molecular oxygen, namely, ethylbenzene conversion remains around 12% with identical selectivity of about 80% for acetophenone even after six-times reuse of the catalyst.

CO_2 hydrogenation to methanol over Cu/Zn/Al/Zr catalysts prepared by liquid reduction

Cu/Zn/Al/Zr catalysts containing Cu in three valence states(Cu2+,Cu+and Cu0)were prepared usinga liquid reduction method and subsequently calcined at different temperatures.The effects of thecalcination temperature on the catalyst structure,interactions among components,reducibility anddispersion of Cu species,surface properties and exposed Cu surface area were systematically investigated.These materials were also applied to the synthesis of methanol via the hydrogenation ofCO2.The results show that a large exposed Cu surface area promotes catalytic CO2conversion andthat there is a close correlation between the Cu+/Cu0ratio and the selectivity for methanol.A calcinationtemperature of573K was found to produce a Cu/Zn/Al/Zr catalyst exhibiting the maximumactivity during the synthesis of methanol.

Kinetics of Treated Domestic Sewage Disinfection through Catalytic Oxidation with H2O2

The inactivation of bacterial cells through catalyzed oxidation using hydrogen peroxide as the primary oxidant agent is dependent on a series of factors, such as the concentration of the catalyst, the rate of hydroxyl radical formation in the controlled decomposition of the oxidant agent, and the concentration and toxicity of hydrogen peroxide. The objective of this study was to develop a mathematical model able to predict the kinetics of the inactivation Escherichia coli and total coliforms cells present in treated domestic sewage through catalytic peroxidation. The catalyst used was iron oxide supported on mineral coal （called CP）, and the effects of the operational conditions, including hydrogen peroxide concentration and dosage of catalyst, were evaluated. The results showed that the disinfection kinetics of the treated domestic sewage is dependent on the concentrations of hydrogen peroxide and catalyst dosage. The kinetic model was shown to be able to predict the behavior of the inactivation kinetics of the bacterium Escherichia coli ATCC-25922 when different concentrations of hydrogen peroxide （75 and 100 mg·L^-1） were used, regardless of the catalyst dosage.

Decomposition of Benzo （a） Pyrene on Artificial Sea Water Using UV/Photocatalytic Oxidation Process

In recent years, serious heavy oil pollution has frequently occurred in the ocean. Heavy oil has escaped from grounded oil carrier and drifted ashore. Drifted heavy oil contains hazardous chemical such as benzo （a） pyrene and other poly aromatic hydrocarbons （PAHs）. These hazardous chemicals have worse affected on sea plants and animals. Thus, it is important to develop effective elimination of hazardous chemicals or drifted petroleum from sea shore. In this study, we have investigated the decomposition of benzo （a） pyrene on artificial sea water using UV/photocatalytic oxidation process. From this study, it was found that about 90% of benzo （a） pyrene on artificial seawater was decomposed by UV/photocatalytic oxidation process. And there were no by-product from decomposition of benzo （a） pyrene. It was supposed that benzo （a） pyrene was completely decomposed using UV/photocatalytic oxidation process.

Multi-objective optimization of p-xylene oxidation process using an improved self-adaptive differential evolution algorithm

The rise in the use of global polyester fiber contributed to strong demand of the Terephthalic acid （TPA）. The liquid-phase catalytic oxidation of p-xylene （PX） to TPA is regarded as a critical and efficient chemical process in industry [ 1 ]. PX oxidation reaction involves many complex side reactions, among which acetic acid combustion and PX combustion are the most important. As the target product of this oxidation process, the quality and yield of TPA are of great concern. However, the improvement of the qualified product yield can bring about the high energy consumption, which means that the economic objectives of this process cannot be achieved simulta- neously because the two objectives are in conflict with each other. In this paper, an improved self-adaptive multi-objective differential evolution algorithm was proposed to handle the multi-objective optimization prob- lems. The immune concept is introduced to the self-adaptive multi-objective differential evolution algorithm （SADE） to strengthen the local search ability and optimization accuracy. The proposed algorithm is successfully tested on several benchmark test problems, and the performance measures such as convergence and divergence metrics are calculated. Subsequently, the multi-objective optimization of an industrial PX oxidation process is carried out using the proposed immune self-adaptive multi-objective differential evolution algorithm （ISADE）. Optimization results indicate that application oflSADE can greatly improve the yield of TPA with low combustion loss without degenerating TA quality.

Electrocatalytic behaviour of Ni and NiCu alloy modified glassy carbon electrode in electro-oxidation of contraflam

The electrocatalytic oxidation of contraflam was investigated in alkaline solution on nickel and nickel–copper alloy modified glassy carbon electrodes(GC/Ni and GC/NiCu). We prepared these electrodes by galvanostatic deposition and the surface morphologies and compositions of electrodes were determined by energy-dispersive X-ray(EDX) and scanning electron microscopy(SEM). Cyclic voltammetry and chronoamperometric methods were employed to characterize the oxidation process and its kinetics. Voltammetric studies exhibit one pair of well-defined redox peaks, which is ascribed to the redox process of the nickel and followed by the greatly enhanced current response of the anodic peak in the presence of contraflam and a decrease in the corresponding cathodic current peak. This indicates that the immobilized redox mediator on the electrode surface was oxidized contraflam via an electrocatalytic mechanism. The catalytic currents increased linearly with the concentration of contraflam in the range of 0.25– 1.5 mmol/L. The anodic peak currents were linearly proportional to the square root of scan rate. This behaviour is the characteristic of a diffusion-controlled process. The determination of contraflam in capsules is applied satisfactorily by modified electrode.