New approach to environmentally benign epoxidation: the solid-phase-system using urea–H2O2 and recyclable dodecatungstate on apatite

On the basis of new concept using a solid disperse phase we have developed an efficient catalytic solid-phase-system for epoxidations of alkenes using urea–hydrogen peroxide (urea–H₂O₂) complex and cetylpyridinium dodecatungstate ((CetylPy)₁₀[H₂W₁₂O₄₂]) catalyst on fluorapatite (FAp). The recovered solid catalyst phase was reused to keep the catalytic activity after several times. In the conceptual idea it is a key point that in situ solid-phase-activation of the catalyst with urea–H₂O₂ proceeds to form microcrystals of the active species dispersed on the solid phase. The dispersion of the catalyst on FAp in the case of tungstic acid (H₂WO₄) was suggested by EPMA analysis. We proposed the peroxo type of species keeping the parent polyoxometalate framework as novel active species from FT-IR spectroscopic studies. FAp phase plays important roles of dispersing the active species on its surface to have high catalytic activity and of stabilizing the active species to lead to high reusability.     

Hydrolysis of Fe(OH)SO4 in the presence of metallic iron

Hydrolysis of Fe(OH)SO₄ was carried out in the presence of metallic iron in order to prevent the formation of iron(III) oxides with strongly bonded sulphate. Under the conditions of the experiment, the products were found to be mixtures of ?-Fe₂O₃ and α-FeOOH. The occluded sulphate, if any, could be easily washed out with water. The hydrolysis reaction passes through an equilibrium state before coming to completion. The entropy with enthalpy of the hydrolysis corresponding to the equilibrium state were found to be 4 e.u. and 0·5 kJ/mol, respectively. The activation energy of the hydrolysis reaction was found to be 21 kJ/mol.     

层状催化剂颗粒的优化设计——双组分等温平行反应体系

针对双组分等温平行反应体系,分析讨论了以提高催化剂活性和选择性为目标时催化剂活性组分的最优分布形式(为δ-函数分布),并给出了确定这种反应体系的催化剂的最佳活性层位置的计算方法。结果表明:以提高选择性为目标的最佳活性层位置比以提高活性为目标的要更靠近催化剂核心,实用的最优位置应介于二者之间。最后,本文还研究了反应动力学级数、本性选择性以及内扩散模数(Thiele 模数)等因素对最佳活性层位置的影响。     

U(Ⅳ)-U(Ⅵ)同位素交换反应动力学研究 Ⅰ.Fe~(2+)对U(Ⅳ)-U(Ⅵ)同位素交换反应的催化作用

一、前言由于U(IV)-U(VI)同位素交换体系具有相当大的同位素效应和很好的稳定性,并且容易实现两相回流,这对于分离U同位素的工业应用都是十分有利的。但是,U(IV)-U(VI)同位素交换反应速度非常慢,常温下H~+浓度为1.0—4.0 mol/l时,速度常数为1.0×10~(-4)l~2/mol·s。因此要用U(IV)-U(VI)交换体系浓缩铀同位素,必须研究U(IV)-U(VI)交换反应动力学,找到加快交换反应的方法。     

Facile optical resolution of amino acid esters via hydrolysis by an industrial enzyme in organic solvents

Racemic amino acid esters were optically resolved via hydrolysis in organic solvents by the catalysis of an industrial alkaline protease, “Alcalase”. The products which were composed mainly of L-amino acids were insoluble and easily separated by filtration. The activity of the enzyme and enantiomeric excess of the products were significantly dependent on the nature of solvent and the water content in the reaction media. Generally, high values of enantiomeric excess were obtained at low water contents. Many natural and unnatural amino acids were resolved by this method.     

Ti-silicalite as catalyst for gas-phase ammoximation of cyclohexanone with molecular oxygen

The catalyst behaviour of titanium silicalite, which was found the most active and selective catalyst for liquid-phase ammoximation of cyclohexanone to the corresponding oxime with hydrogen peroxide, was investigated in the gas-phase ammoximation with molecular oxygen in and compared with those of pure silicalite and samples of vanadium and chromium silicalites. The results showed that Ti-silicalite is a selective catalyst not only in the reaction with hydrogen peroxide but also in the reaction with molecular oxygen. However, a big limitation was found in the poor activity of the silicalites which do not allow to reach high oxime yields.     

悬浮床加氢裂化油溶性催化剂与沥青质的作用

在高压釜反应器中对添加了油溶性 Ni 催化剂(UPC-O)和水溶性 Ni 催化剂(UPC-W)的辽河稠油常压渣油(LHAR)进行了悬浮床加氢裂化实验。通过元素分析和傅里叶变换红外光谱(FTIR)分析对抑制反应生焦效果好的 UPC-O 与 LHAR 沥青质的作用进行了研究。元素分析结果显示,在 LHAR 中加入 UPC-O1000μg/g,沥青质和脱沥青质油中 Ni 含量分别出476μg/g和110μg/g 增加到7 559μg/g 和1 024μg/g,表明 UPC-O 在沥青质中有富集的趋势。FTIR 表征结果显示,UPC-O 和沥青质发生了相互作用。UPC-O 可在沥青质原位硫化为活性组分,对沥青质在悬浮床加氢裂化反应中的缩合起到好的抑制作用。     

Syngas production via combined oxy-CO2 reforming of methane over Gd2O3-modified Ni/SiO2 catalysts in a fluidized-bed reactor

In this research, Ni/SiO₂ catalyst was modified with different amount of Gd₂O₃ and characterized with temperature-programmed desorption of CO₂ (CO₂-TPD) and NH₃ (NH₃-TPD), temperature-programmed reduction with H₂ (H₂-TPR) and X-ray diffraction (XRD). It was found that Gd₂O₃-modified Ni/SiO₂ catalysts possessed higher CO₂ adsorption and activation ability due to the formation of surface carbonate species. H₂-TPR and XRD characterizations found that the strong interaction among nickel, Gd₂O₃ and SiO₂ took place, which improved the dispersion of Ni. Gd₂O₃-modified Ni/SiO₂ catalysts exhibited higher activity and stability for the combined oxy-CO₂ reforming of methane in fluidized-bed reactor. The H₂/CO ratio in produced syngas could be controlled via controlling reaction temperature and CO₂/O₂ ratio in feed.     

Effect of carbon surface oxidation on platinum supported carbon particles on the performance of gas diffusion electrodes for the oxygen reduction reaction

The effect of carbon surface oxidation on platinum supported carbon particles (Pt/C) with nitric acid was investigated by cyclic voltammetry, electrochemical impedance spectroscopy, polarization experiments and chronoamperometry. Cyclic voltammograms, polarization curves and electrochemical impedance spectra showed that the treated catalyst had much larger active surface area and higher ionic conductivity than the untreated catalyst, and provided enhanced performance for oxygen reduction. The formation of acidic groups was examined by IR spectra. The Pt/C surface oxidation had a large effect on the performance of a gas diffusion electrode for oxygen reduction reaction.     

Antimicrobial finishing of regular and modified polyethylene terephthalate fabrics

An effective two-stage method has been developed for imparting antimicrobial properties to regular polyethylene terephthalate (R-PET), polyethylene glycol modified polyethylene terephthalate (PEG-M-PET), R-PET/Cotton blend (R-PET/C) and PEG-M-PET/Cotton blend (PEG-M-PET/C) fabrics. The method consists of partial hydrolysis of the fabrics to create carboxylic groups in PET macromolecules followed by subsequent reaction with dimethylalkylbenzyl ammonium chloride (DMABAC) under alkaline conditions. The reaction conditions such as pH, reaction temperature and time, carboxylic content, and DMABAC concentration were studied. Characterization of the finished fabrics was carried out through scanning electron microscopy (SEM) and Fourier transform infrared spectra (FTIR). All the modified PET fabrics showed excellent antibacterial activity towards Gram-positive (Bacillus mycoides), Gram-negative (Escherichia coli), and nonfilamentous fungus (Candida albicans). The achieved antimicrobial functions on the PET fabrics are durable in repeated laundering processes. Even after laundering 10 times the fabrics could still provide more than 85% of its antimicrobial activity against B. mycoides, E. coli, and C. albicans. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008