环戊烯催化氧化合成戊二醛及其动力学

对在非水溶剂存在下过氧化氢一步催化氧化环戊烯制备戊二醛过程中的催化体系进行了研究。考察了具有脱水功能的Ｂ２Ｏ３的作用及用量，确立了具有优良催化性能的催化体系ＷＯ３－Ｂ２Ｏ３；实验测定了反应动力学数据，采用非线性回归Ｐｏｗｅｌ共扼法求得了反应动力学方程。在推荐的催化剂体系和工艺条件下，环戊烯转化率６７％，戊二醛收率６３％，选择性９１％。     

Comparison of a contactor catalytic membrane reactor with a conventional reactor: example of wet air oxidation

A wet air oxidation reaction was carried out in a gas/liquid catalytic membrane reactor of the contactor type. The oxidation of formic acid was used as a model reaction. The mesoporous top-layer of a ceramic tubular membrane was used as catalyst (Pt) support, and was placed at the interface of the gas (air) and liquid (HCOOH solution) phases.

A similar reaction was carried out in a conventional batch reactor, using a steering rate high enough to avoid gas-diffusion limitations, and exactly identical conditions than for the CMR (amount of catalyst, pressure, etc.). At room temperature, the CMR showed an initial activity three to six times higher than the conventional reactor. This activity increase was attributed to an easier oxygen access to the catalytic sites. Nevertheless, the catalytic membrane gradually deactivated after a few hours of operation. Different deactivation mechanisms are presented.     

Ni-ZrO2纳米复合电铸层抗高温氧化性能的研究

通过间歇式抗高温氧化实验,建立了纯镍电铸层和N i-ZrO2纳米复合电铸层高温氧化动力学模型,分析了电铸层表面和横截面的形貌,测定了电铸层的组织结构。结果表明,N i-ZrO2纳米复合电铸层抗高温氧化性能明显优于纯镍铸层,复合电铸层表面生成的氧化膜晶粒细小且致密,并且该氧化膜较薄,产生的内应力较小,与复合电铸层的黏附性较好。     

Liquid-phase oxidation of toluene by molecular oxygen over copper manganese oxides

Copper manganese oxides (Cu–Mn oxides) were prepared by coprecipitation method and characterized by several techniques, such as X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and Temperature-programmed reduction (TPR). Catalytic activities of the Cu–Mn oxides were tested by the oxidation of toluene with molecular oxygen in liquid phase and solvent-free conditions. The molar ratio of Cu:Mn in catalyst was optimized to be 1:1 and thus the corresponding crystalline material was designated as Cu_1.5Mn_1.5O₄.     

Oxidative flavour deterioration of fish oil enriched milk

The oxidative deterioration of milk emulsions supplemented with 1.5 wt‐% fish oil was investigated by sensory evaluation and by determining the peroxide value and volatile oxidation products after cold storage. Two types of milk emulsions were produced, one with a highly unsaturated tuna oil (38 wt‐% of n‐3 fatty acids) and one with cod liver oil (26 wt‐% of n‐3 fatty acids). The effect of added calcium disodium ethylenediaminetetraacetate (EDTA) on oxidation was also investigated. Emulsions based on cod liver oil with a slightly elevated peroxide value (1.5 meq/kg) oxidised significantly faster than the tuna oil emulsions, having a lower initial peroxide value (0.1 meq/kg). In the tuna oil emulsions the fishy off‐flavour could not be detected throughout the storage period. Addition of 5—50 ppm EDTA significantly reduced the development of volatile oxidation products in the cod liver oil emulsions, indicating that metal chelation with EDTA could inhibit the decomposition of lipid hydroperoxides in these emulsions. This study showed that an oxidatively stable milk emulsion containing highly polyunsaturated tuna fish oil could be prepared without significant fishy off‐flavour development upon storage, provided that the initial peroxide value was sufficiently low.     

Single-phase gold/palladium catalyst: The nature of synergistic effect

The liquid phase oxidation of glycerol with oxygen has been studied using mono and bimetallic catalysts based on Au and Pd metals supported on activated carbon, in order to study the effect of the metal on the distribution of the products and on activity of catalysts. It was found that by using bimetallic catalysts (Au–Pd) a strong synergistic effect was shown. By using a preformed nucleating centre we were able to obtain a single alloyed phase, which allowed us to address the synergistic effect to the presence of alloyed Au/Pd. The advantage of using this latter catalyst lies not only in the high activity but also in a prolonged catalyst life. Although a partial leaching of palladium and assembling of the particles have been revealed by ICP and HRTEM respectively, activity after 10 re-cycles decreased less than expected (about 10%).     

钒硅中孔分子筛的合成、表征及其催化性能研究

在碱性环境中，采用水热合成法制备得到了不同硅钒比的钒硅中孔分子筛V－MCM－41，利用XRD，IR，TG等表征方法考察了钒的搀杂量与其结构和性能之间的关系，该催化剂对苯乙烯氧化反应具有较好的催化活性，在一定的反应条件下，以H2O2溶液（30％）为氧化剂，以乙腈为溶剂，V－MCM－41（Si/V=25)能使苯乙烯的转化率达到95％以上，产物（苯甲醛＋苯甲酸）的选择性不低于90％。     

Platinum particle size effect on the oxidative dehydrogenation of aqueous ethanol

The effect of the platinum particle size was investigated for the catalytic oxidative dehydrogenation of aqueous ethanol to ethanal at a temperature of 303 K, an ethanol concentration of 260 mol m^–3, a partial oxygen pressure 60 kPa, a pH of 9, and an ethanal and ethanoate concentration of 20 mol m^–3. A particle size effect on the turnover frequency was observed but only for particle sizes smaller than 2 nm. Hence, the reaction shows a limited structure sensitivity.     

Effect of Addition of Oxides on Low-Temperature Oxidation of Molybdenum Disilicide

A type of aluminosilicate that has a good wetting property for molybdenum disilicide (MoSi₂) was added to a MoSi₂ matrix to study the effects on the microstructure and low-temperature oxidation. It was found that the composites had not only good low-temperature oxidation resistance but also high thermal shock resistance when the added oxides formed a network microstructure in the matrix. There was no appreciable oxidation gain for MoSi₂/oxide composites with a network microstructure at 773 K for 2500 h. The results indicate that microstructure design is a simple and effective solution to preventing the low-temperature oxidation of MoSi₂.     

在VPO催化剂上丁烷选择氧化的质谱研究

The selective oxidation of n-butane to maleic anhydride(MA) on a vanadium-phosphorus oxide (VPO) catalyst was studied using on-line gas-chromatography combined with mass spectrometry(GC-MS) and transient response technique.The reaction intermediates,butene and furan,were found in the reaction effuent under near industrial feed condition (3% butane 15% O2),while dihydrofuran was detected at high butane concentration (12% butane,5%O2).Some intermediates of MA decomposition were also identified.Detection of these intermediates shows that the vanadium phosphorus oxides are able to dehydrogenate butane to butene,and butene further to form MA.Based on these observations,a modified scheme of reaction network is proposed.The transient experiments show that butane in the gas phase may directly react with oxygen both on the surface and from the metal oxide lattice,without a proceeding adsorption step.Gas phase oxygen can be adsorbed and transformed to surface lattice oxygen but it can not participate in selective oxidation.Adsorbed oxygen leads to deep oxidation,while lattice oxygen leads to selective oxidation.