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.     

臭氧氧化处理法对聚丙烯表面涂装性的改良 Ⅱ.臭氧浓度及臭氧发生气组成对聚丙烯表面氧化过程的影响

讨论了用臭氧氧化法对聚丙烯表面进行涂装性改良时,臭氧浓度和臭氧发生气组成对聚丙烯表面氧化过程的影响。我们发现,随臭氧浓度的增加,各种聚丙烯表面上COOH基的生成速率变大,而OH基的生成速率变小,且表面上COOH基和OH基的生成比变大。在相同的臭氧浓度下,COOH基的生成速率和聚丙烯种类无关,各种聚丙烯表面上COOH的生成速率大体相等。而OH基的生成速率及COOH基、OH基生成比和聚丙烯的种类有关,就COOH基和OH基生成比而言,其大小顺序为均聚物>嵌段共聚物>无规共聚物。臭氧发生气组成对聚丙烯表面氧化过程有很大的影响。和臭氧发生气为空气时的情况相比,当臭氧发生气为氧气时,即使其体系中臭氧浓度的变化很小,也会引起较大的表面氧吸收量或表面氧化分解量的变化。     

Characterization and Catalytic Properties of Combustion Synthesized Au/CeO2 Catalyst

Ceria-supported Au catalyst has been synthesized by the solution combustion method for the first time and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Au is dispersed as Au⁰ as well as Au³⁺ states on CeO₂ surface of 20-30 nm crystallites. On heating the as-prepared 1% Au/CeO₂ in air, the concentration of Au³⁺ ions on CeO₂ increases at the expense of Au⁰. Catalytic activities for CO and hydrocarbon oxidation and NO reduction over the as-prepared and the heat-treated 1% Au/CeO₂ have been carried out using a temperature-programmed reaction technique in a packed bed tubular reactor. The results are compared with nano-sized Au metal particles dispersed on -Al₂O₂ substrate prepared by the same method. All the reactions over heat-treated Au/CeO₂ occur at lower temperature in comparison with the as-prepared Au/CeO₂ and Au/Al₂O₂. The rate of NO + CO reaction over as-prepared and heat-treated 1% Au/CeO₂ are 28.3 and 54.0 mol g^-1 s^-1 at 250 and 300 °C respectively. Activation energy (E _a) values are 106 and 90 kJ mol^-1 for CO + O₂ reaction respectively over as-prepared and heat-treated 1% Au/CeO₂ respectively.     

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.