镧系钙钛矿型氧化物（LaBO3）的催化氧化性能及其净化效果的研究

本文在气相色谱仪联用微反应器装置上,研究了LaBO_3型催化剂中的B位元素对催化氧化活性的影响规律,并进行了程序升温脱附实验。另外,还对LaBO_3型载体催化剂进行了活性筛选,并在柴油机台架上与贵金属Pt/Al_2O_3进行了有害气体净化效果的对比实验。实验结果表明,LaBO_3氧化物中LaMnO_3对CO、CH_4的催化氧化活性最高,且CO、CH_4活性中心并不一致。LaMnO_3/γ-Al_2O_3浸渍微量助化剂后,能使CO在130℃完全氧化,CH_4的氧化温度在300～500℃范围内,LaMnO_3载体催化剂对柴油机有害排放物的净化率很低,浸渍微量助化剂后,净化率提高一倍以上,特别是LaMnO_3/堇青石蜂窝陶瓷,浸渍后的净化效果同贵金属Pt/Al_2O_3接近。     

A FT-IR assessment of iso-C4H8 reactivity with V2O5/TiO2 catalysts

Low-loaded vanadia-titania catalysts have been prepared by impregnation of titania P-25 (Degussa). The catalysts were characterized by X-ray diffraction, specific surface area and porosity assessment by nitrogen adsorption at 77 K. For very low vanadia contents the absence of surface acid Brønsted sites leads to dimerization on surface acid Lewis sites, whereas the presence of surface acid Bransted sites when the vanadia content is increased leads to oxidation to carbonyl and carboxylate species.     

Some kinetic aspects of unsteady-state partial oxidation reactions. Dynamic processes on metal oxide surfaces

It is shown that steady-state kinetic data do not allow the discrimination between the redox and associated mechanisms of the partial oxidation reactions. A discrimination between these mechanisms was performed using transient experiments. The obtained rate expressions are in agreement with experimental kinetic data for catalytic partial oxidation of o-xylene.

An influence of the conjugate oxidation of a catalyst surface on dynamics and kinetics of the heterogeneous catalytic oxidative reactions is considered. Computing simulation of methane oxidative coupling of methane reaction at lowered temperature and elevated pressure has been performed. It showed that the reaction order with respect to oxygen exceeding unity is consistent with the chain branching mechanism of the reaction in the presence of TiSi₂ and TiB₂ and showed the important role of the branching chain cycles in the low-temperature OCM reaction at elevated pressure.     

氧化铝丝的研制

氧化铅丝生产过程中最关键的工艺是连续阳极氧化。氧化膜击穿电压决定于氧化膜厚度。控制膜厚度的三要素为:电解液(成份、浓度及温度),槽电压和铝丝走速。     

Effect of maillard reaction volatile products on lipid oxidation

Maillard reaction volatile compounds (MRV), prepared by heating a glucose-glycine solution, were tested as antioxidants in soybean oil (SBO) thermoxidation. The volatiles were transferred into the oil by stripping with a stream of Nitrogen and substituting the atmosphere above the oil with air containing MRV. Standard accelerated oxidation was performed by heating the SBO. Peroxide value measurement and headspace gas Chromatographic analysis were carried out on all the samples. The MRV antioxidant activity was evaluated by determining the effect of the induction period and the kinetic rate constant of peroxide and oxidation volatiles formation. The MRV showed a significant antioxidant activity. The effectiveness was variable depending on MRV transfer method to the oil, and the Maillard reaction extent was related to the browning level of glucose/glycine solution. It was found that the maximum effect of MRV prolonged about three times the induction period and reduced the kinetic rate constant by half in relation to the control sample. MRV affects oxidative stability of soybean oil by lengthening the induction period as well as by decreasing the rate of oxidation at the propagation state and reducing the formation of hexanal.     

Technique for Producing Mullite and Other Mixed-Oxide Systems

Mixed-oxide systems are of interest in a variety of technical ceramic applications. The key in many systems is to achieve a high degree of homogeneity, approaching the molecular level. A technique for producing mixed oxides via direct oxidation of mixtures of organometallic compounds is discussed as a potential route. Preliminary work performed on producing mullite is discussed.     

Selective partial oxidation of light paraffins with hydrogen peroxide on thin-layer supported Nafion-H catalysts

Thin-layer carbon supported Nafion-H catalysts were found to be active and highly selective (S>98%) for the partial oxidation of C₁-C₃ alkanes, in a three phase catalytic membrane reactor (3PCMR), under mild conditions and in the presence of H₂O₂. The influences of the catalyst teflon loading and H₂O₂ concentration on the reaction rate have been evaluated. A reaction pathway, based on the electrophilic hydroxylation of the C-H bond of alkanes with protonated hydrogen peroxide (H₃O ₂ ⁺ ), is discussed.     

Yttrium sol–gel coating effects on the cyclic oxidation behaviour of 304 stainless steel

The present results reveal the interest of sol–gel coating technique to improve 304 steel high temperature oxidation resistance. An yttrium sol–gel coating appears to enhance the oxidation resistance during isothermal oxidation test, to decrease widely the oxide weight gain and to reduce the initial transient oxidation stage generally observed in the case of blank steels. Moreover, the experimental results confirm that yttrium sol–gel coating also plays a significant role on the cyclic oxidation behaviour of the 304 steel. In fact, the yttrium addition promotes remarkably the prolongation of the period during which the oxide scale still remains adherent to the substrate.     

Photoelectrocatalytic humic acid degradation kinetics and effect of pH,applied potential and inorganic ions

This study addresses the removal of humic acid (HA) dissolved in an aqueous medium by a photoelectrocatalytic process. UV₂₅₄ removal and the degradation of color (Vis₄₀₀) followed pseudo‐first order kinetics. Rate constants were 1.1 × 10^?1 min^?1, 8.3 × 10^?2 min^?1 and 2.49 × 10^?2 min^?1 (R² > 0.97) for UV₂₅₄ degradation and 1.7 × 10^?1 min^?1, 6.5 × 10^?2 min^?1 and 2.0 × 10^?2 min^?1 for color removal from 5 mg dm^?3, 10 mg dm^?3 and 25 mg dm^?3 HA respectively. Following a 2 h irradiation time, 96% of the color, 98% of the humic acid and 85% of the total organic carbon (TOC) was removed from an initial 25 mg dm^?3 HA solution in the photoanode cell. Photocatalytic removal on the same photoanode was also studied in order to compare the two methods of degradation. Results showed that the photoelectrocatalytic method was much more effective than the photocatalytic method especially at high pH values and with respect to UV₂₅₄ removal. The effect of other important reaction variables, eg pH, external potential and electrolyte concentration, on the photoelectrocatalytic HA degradation was also studied. Copyright © 2003 Society of Chemical Industry     

On the kinetics of the autoxidation of fats: influence of pro‐oxidants,antioxidants and synergists

The influence of minor amounts of pro‐ and anti‐oxidants on the kinetics of the autoxidation of fat has been evaluated. The reaction rates of oxygen with the substrates were found to follow the same basic equation, hitherto established for pure substrates. There is evidence that the surface of the reaction vessel also acts as a reaction catalyst and its effect is proportional to the area of glass in contact with lipids. Oxidation is enhanced by trace metal ions as well as by surface‐active compounds (e.g. hydroperoxides and sterols). Antioxidants such as α‐tocopherol and butylated hydroxyanisole inhibit the oxidation by delaying the start of oxygen consumption (the induction period) while retarders like amino acids only decrease the rate of oxidation. Thus pro‐ and anti‐ oxidants affect either the start or the rate of oxygen consumption. The empirical formula dx/dt = k [O₂] (1‐x/n) f′(t) was found applicable to the different stages of oxidation.