Selective solvation of polystyrene in tetralin/cyclohexane mixtures

Refractive index increments and density increments have been measured at 307.6K for polystyrene in binary solvents of 1,2,3,4-tetrahydronaphthalene (tetralin, TET) and cyclohexane over the whole range of solvent composition. Comparison of these increments with the corresponding values obtained at dialysis equilibrium (i.e. at constant chemical potential of low molecular weight species) yielded the coefficients of selective adsorption (γ₁) of TET by the polymer. Positive values of γ₁ were exhibited at solvent compositions up to 78% (v/v) of the thermodynamically better solvent, TET. Theoretical curves of γ₁ vs. composition were calculated on the basis of, firstly, relevant interaction parameters and, secondly, interaction parameters in conjunction with solubility parameters. Both procedures afforded self-consistent results, which were, however, uniformly lower than the experimental values of γ₁.     

DIRECT OXIDATION OF ETHYLENE TO ACETALDEHYDE IN A HOLLOW FIBER MEMBRANE REACTOR†

A hollow fiber membrane reactor, which resembles a tube-and-shell heat exchanger, was developed for homogeneous catalytic reactions with gas reactants and products. The gas stream flows through the tube side while the reaction takes place in the catalyst solution which fills the shell side. The separation load of product from the catalyst solution can be reduced by using a hollow fiber membrane reactor instead of a conventional bubble column reactor. The reactor operates in a plug-flow pattern with a large mass transfer area per unit volume of catalyst solution

This concept was investigated experimentally using the direct oxidation of ethylene to acetaldehyde reaction in an aqueous solution of palladium (H) chloride-cupric chloride with a silicone rubber membrane reactor and a polypropylene membrane reactor. It was experimentally demonstrated that membrane reactors could achieve higher production rates per unit volume of catalyst than the conventional sparged reactor. The experimental data were in good agreement with the predictions by the mathematical model. The conditions under which the membrane reactor will be more advantageous than the conventional sparged reactors can be readily ascertained with the analytical solution of the simplified membrane reactor model.     

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.     

Kinetics of the methanation of carbon dioxide over a supported Ni-La2O3 catalyst

The kinetics of the methanation of carbon dioxide was investigated using an alumina supported Ni-La₂O₂ catalyst in a differential and integral reactor. In the differential reactor the molar ratio of H₂ to CO₂ was varied from 0.6 to 30. In the integral reactor the rates were measured with up to 90% conversion. Both reactor tests were carried out at temperatures between 513 and 593 K. The experimental results were described by a Langmuir-Hinshelwood type equation. The kinetics can be explained by assuming equilibrium of dissociative carbon dioxide and hydrogen adsorption, and assuming hydrogenation of surface carbon as the rate determining step.     

IR study of the interaction of hydroxyl groups of silica gel with Cr species of Phillips' type catalysts

Spectroscopic evidence for the interaction of hydroxyl groups and chromium ions was obtained using a catalyst prepared from chromyl chloride. A new OH peak, observed at 3705 cm^–1 after pumping away CO gas, is attributed to the direct interaction of OH with the low-valent chromium. This peak shifts to 3590 cm^–1 on contact with O₂ at room temperature and it is assigned to a hydroxyl interacting with the oxidized chromium. New assignments are also proposed for IR bands of CO presorbed on the catalyst. The peak due to CO at 2188 cm^–1 decreases as the OH intensity at 3705 cm^–1 increases, suggesting that the former peak arises from adsorption on Cr(II) species to which two oxygen atoms are attached.     

Surface and subsurface products of the interaction of O2 with Ag under catalytic conditions

Polycrystalline Ag treated with O₂ at pressures up to 1 bar and at temperatures up to 920 K was examined by TDS. It was found that the peak commonly observed at 595±25 K and assigned to adsorbed atomic oxygen (O_a) is shifted to higher desorption temperatures with rising dosing temperatures. Since saturation of the uptake was not possible either, this peak was identified as dissolved atomic oxygen (O_d). The existence of a maximum for the O₂ uptake after exposure at 820 K was found. Hence, under conditions of formaldehyde synthesis ( 920 K) the ability of the catalyst to dissolve oxygen is near its maximum.     

环氧丙烷生产工艺进展

综述了近年来环氧丙烷合成工艺的新进展,包括对现有环氧丙烷生产工艺的革新、直接氧化法、光催化环氧化等方法,并对各种方法的特点和发展前景进行了讨论.     

Effect of particle size on the surface oxidation and flotation behavior of galena particles in lime system

ABSTRACT

In this research, the effect of particle size on the surface oxidation and flotation behavior of galena in the lime system was studied. Coarse (?0.074 + 0.038 mm), intermediate (?0.038 + 0.025 mm) and fine (?0.025 mm) galena particles were used in the experiment. The dissolution tests, flotation tests, and sorption tests were accomplished. Through further analysis by XPS, the effect of particle size and lime was observed. The decrease of mineral particle sizes increased the adsorption ratio of collector and the dissolution of galena, while the hydrophilic product OH^?/Ca(OH)⁺ produced by dissolution occupied the dominant position, which led to the minerals hydrophilic.     

基于中红外QCL的痕量CO气体传感器

为了减少CO爆炸给国民经济造成的巨大损伤,提出了一种能够快速地监测环境空气中痕量CO的气体传感器。由于CO分子基频吸收谱带的吸收线强要比泛频带和组合频带的吸收线强高出2～3个数量级,选择激射中心波长为4.65μm中红外量子级联激光器（QCL）作为光源,同时再配合长光程Herriott气室提高了CO体积分数检测下限。同时,该传感器采用单光源双探测器差分光学结构,消除了电调制光源所带来的不稳定性。实验表明：该传感器CO体积分数检测下限为2×10-6,并且操作人员可以通过替换在不同波长下运行的中红外QCL来测量其它气体。     

甲酸甲酯合成与转化的催化技术

本文评述了甲酸甲酯(MF)合成与转化的催化技术,展示了从MF出发发展C_1化学的可能途径,在MF的合成方面详细地分析了从甲醇出发的羰化法、脱氢法和氧化法催化技术,简介了我们的有关研究工作。