甲烷一步氧化制甲醇新技术进展

主要介绍国内外关于甲烷直接氧化制甲醇新技术研究进展,包括生物催化,仿生催化,光催化,冷等离子技术及超临界与膜的应用等。     

Production of hydrogen over bimetallic Pt–Ni/δ-Al2O3: I. Indirect partial oxidation of propane

Indirect partial oxidation (IPOX) of propane was studied over bimetallic 0.2 wt.% Pt–15 wt.% Ni/δ-Al₂O₃ catalyst in the 623–743 K temperature range. The unreduced and reduced forms of the catalyst were characterized by ESEM–EDAX and X-ray diffraction (XRD). In the IPOX tests, the effects of steam to carbon ratio (S/C), carbon to oxygen ratio (C/O₂) and residence time (W/F (g_cat h/mol HC)) on the hydrogen production activity, selectivity and product distribution were studied in detail. The effect of temperature program applied (increasing from 623 to 743 K, ITP; decreasing from 743 to 623 K, DTP) during reaction was also tested. The results showed that the Pt–Ni bimetallic system has superior performance characteristics compared to the monometallic catalysts reported in literature. The reason is thought to be the utilization of the catalyst particles as micro heat exchangers during IPOX; the heat generated by Pt sites during exothermic total oxidation (TOX) being readily transferred through the catalyst particles acting as micro heat exchangers to the Ni sites, which promote endothermic steam reforming (SR). The optimal conditions were found as S/C = 3, C/O₂ = 2.70 and W/F = 0.51 g_cat h/mol HC for IPOX of propane on the basis of high hydrogen productivity and selectivity between 623 and 748 K for the experimental conditions tested. The thermo-neutral points obtained showed the sustainability of reaction in terms of energy.     

难处理金矿石加石灰焙烧焙砂中CaS的消除

介绍了用空气氧化预浸加石灰焙烧焙砂中的CaS，以消除其对金氰化的影响。预浸后金的氰化浸出率可从58％提高到80％以上。     

润滑油抗氧剂的作用机理

简介了润滑油使用过程中导致其氧化的影响因素和所形成氧化物对使用性能的影响，以及润滑油基础油的氧化机理，叙述了酚类、胺类、有机铜盐、有机硫、烷基硫代氨基甲酸盐、有机磷、硫代苯并三氮唑、硒化物抗氧剂的抗氧化作用机理。     

Catalytic oxidation of sulfide ions over nickel hydroxides

The catalytic sulfide ion oxidation by oxygen to elemental sulfur over β-Ni(OH)₂ and LiNiO₂ has been studied. As a result of experimental investigation performed, a reaction mechanism is suggested which involves heterogeneous and homogeneous processes. Dioxygen activation in the heterogeneous process proceeds via a redox Ni²⁺ ↔ Ni³⁺ transition and participation of OH⁻ groups. The active HO⁻₂ species thus formed carries on the reaction in homogeneous phase. Nickel hydroxides are promising catalysts for practical application.     

Reactivity of steam in exhaust gas catalysis III. Steam and oxygen/steam conversions of propane on a Pd/Al2O3 catalyst

A 1% Pd catalyst (38% dispersion) was prepared by impregnating a γ-alumina with palladium acetylacetonate dissolved in acetone. The behaviour of this catalyst in oxidation and steam reforming (SR) of propane was investigated. Temperature-programmed reactions of C₃H₈ with O₂ or with O₂ + H₂O were carried out with different stoichiometric ratios S(S =[O₂]/5[C₃H₈]). The conversion profiles of C₃H₈ for the reaction carried out in substoichiometry of O₂ (S < 1) showed two discrete domains of conversion: oxidation at temperatures below 350°C and SR at temperatures above 350°C. The presence of steam in the inlet gases is not necessary for SR to occur: there is sufficient water produced in the oxidation to form H₂ and carbon oxides by this reaction. Contrary to what was observed with Pt, an apparent deactivation between 310 and 385°C could be observed with Pd in oxidation. This is due to a reduction of PdO_x into Pd⁰, which is much less active than the oxide in propane oxidation. Steam added to the reactants inhibits oxidation while it prevents the reduction of PdO_x into Pd⁰. Compared to Pt and to Rh, Pd has a higher thermal resistance: no deactivation occurred after treatment up to 700°C and limited deactivation after treatment up to 900°C, provided that the catalyst is maintained in an oxygen-rich atmosphere during the cooling.     

Mechanical degradation of coating systems in high temperature cyclic oxidation

Cyclic oxidation tests were performed on a large variety of commercially available overlay coatings. The results of cyclic oxidation tests confirmed that the composition of the coating as well as the processing method of the coating can affect the life of the system. Coating life was determined by the time to coating penetration and initiation of substrate attack. As this work was part of a effort to evaluate the relative protectiveness of available coating systems for Industrial Gas Turbine applications at relatively high temperature, an extensive testing programme was undertaken. The different coatings were tested to visual failure. The results presented in this paper concentrate on the surface instability of the coating. Apart from usual oxidation of the coating an additional degradation mechanism was observed. A mechanical effect caused by the instability of the coating as a result of the difference in the thermal coefficient of expansion and mechanical properties between the substrate and coating. This effect, the so-called “rumpling” effect, resulted in a significant reduction in time to penetration and was in some systems the life controlling factor.     

Alkali-metal Na Adsorption and Promoted Oxidation on Si(100)2×1 Surface

The alkali-metal Na adsorption on Si(100)2×1 surface and its promoted oxidation and Si oxidegrowth have been investigated by means of thermal desorption,work function,Auger electronspectroscopy and photoemission electron spectroscopy.The experimental data showed that therewas a new state,interface electron state,near the Fermi level after the deposition of Na atoms.It wasfound that the presence of Na always caused an increase of the oxygen initial uptake whereas thepromotion of Si oxide growth was observed only at the coverage of Na greater than 0.5 ML.A newmechanism of Na-promoted Si oxide growth is suggested in this paper.     

Storage Stability of Antioxidant-Washed Myofibrils From Chicken White and Red Muscle

Oxidation and gel-forming ability of chicken white (breast) and red (leg) muscle myofibrillar proteins during storage at 0°C were examined. Breast myofibril gels exhibited greater shear moduli than leg myofibril gels throughout 8 days storage. Shear moduli of both breast and leg gels in the intermediate temperature zone (45–55°C) decreased during storage, but at >55°C, they either increased or remained unchanged. Lipid oxidation was inhibited by washing myofibrils with antioxidants propyl gal-late, ascorbate, and tripolyphosphate. However, these antioxidants did not affect the content of protein carbonyls, and only slightly decreased the amine content during storage. Storage affected the kinetic process of myofibril gelation independently of antioxidant treatments.     

乙烯氧化制环氧乙烷固定床反应器的模拟及稳定性分析

在筛选出合适的乙烯氧化制环氧乙烷动力学方程的基础上,对工业固定床氧化反应器进行一维和二维模型的模拟计算。考察操作工艺参数对反应器稳定性、转化率影响的敏感性以及N_2和CH_4做致稳气时反应温度和转化率的轴向、径向分布。