甲醇燃料车尾气净化催化剂的研究Ⅰ.氧含量对钯催化剂上甲醇低温深度氧化性能的影响

甲醇燃料车尾气净化催化剂的研究Ⅰ．氧含量对钯催化剂上甲醇低温深度氧化性能的影响朱兵汪仁（华东理工大学工业催化研究所，上海２００２３７）关键词甲醇燃料，汽车尾气，深度氧化，钯催化剂，氧含量甲醇作为车用汽油代用燃料已在美国、日本、德国等发达工业国家...     

一种甲醇直接气相羰基化新催化剂

本世纪７０年代Ｍｏｎｓａｎｔｏ公司成功开发了甲醇液相羰化ＲｈＩ催化体系，使甲醇羰化生产醋酸成为重要的工业过程．然而，由于此工艺产物与催化剂分离复杂、铑资源紧缺以及体系中还必须加大量的碘甲烷（或氢碘酸）作促进剂，设备腐蚀严重．８０年代以来，甲醇气相羰...     

尿素水解均匀沉淀法制Cu/ZnO/Al2O3甲醇合成催化剂

甲醇是富氯液体，可通过水蒸气重整制氢用于燃料电池的氢源，是最有希望成为燃料电池电动汽车的燃料，目前这方面的研究颇受重视。现代甲醇工业是通过合成气在催化剂作用下反应制得的，所用催化剂主要为Cu／ZnO／Al2O3。为了进一步提高催化剂的性能，近年来关于催化剂制备方法的文献发表较多。吴晓晖等考察了草酸盐胶体法制备Cu／ZnO／Al2O3甲醇合成催化剂的性能，洪中山等用凝胶网格共沉淀法制得Cu／ZnO／Al2O3甲醇合成催化剂，郭宪吉等则考察了添加Mn助剂对Cu／ZnO／Al2O3甲醇合成催化剂的影响。     

低压加氢法制备1,4-环己烷二甲醇的研究

1,4-环己烷二甲醇是生产改性聚酯的中间单体。采用铜系催化剂，以1,4-环己烷二甲酸二甲酯为原料，低压加氢生成1,4-环己烷二甲醇。考察了反应温度、反应压力等对反应活性的影响，进行了200 h的催化剂寿命评价，并对催化剂进行了表征。结果表明，在反应温度200 ℃，反应压力3.0 MPa的条件下，1,4-环己烷二甲酸二甲酯的转化率大于95%，1,4-环己烷二甲醇的选择性大于98%，XRD谱图说明金属铜是该催化剂的主要活性中心。     

Ni整体型催化剂大空速甲烷自热氧化制合成气

随着石油资源的逐渐减少,天然气将是未来基本化学品的主要碳源.因此,天然气的开发利用已日益受到世界范围的广泛重视.当前,天然气的化工利用主要是用于生产合成气,再由合成气制取大量化学品,如合成氨、甲醇和烃类等.目前,工业上生产合成气主要采用水蒸气催化重整工艺.     

甲醇催化脱氢反应的研究

目前工业上，甲醛是使用电解银催化剂或铁铂氧化物催化剂由甲醇氧化脱氢而生产的，氧化脱氢法所制得的甲醛含水量高达60％（质量分数），浓缩需耗费能源，且性能不稳定，又容易生成副产物甲酸，不好应用．另一方面，近年来，在合成化学中如合成性能优良的工程塑料，合成乌洛托品药物等．要求忌水的甲醛的领域显著地增大，这些情况促进生产甲醛的新工艺和新型催化剂的开发研究．1926年Gbosh和Baski报导，在200℃下甲醇几乎全部转化为甲醛．近来报导门要求反应在500oC以上．甲醇究竟应在什么温度下才有显著的直接脱氢的可能性？使用怎么样的…     

阳离子树脂催化合成古龙酸甲酯的动力学研究

古龙酸甲酯化反应是生产维生素C的一个重要中间过程,目前工业上主要采用古龙酸和甲醇为原料,以浓硫酸作催化剂催化酯化.这一反应存在副反应较多,甲酯的色泽深,质量差,后续反应中需用碱进行中和等缺点,给后续处理带来困难.     

甲基叔丁基醚(MTBE)的合成

介绍了甲醇、异丁烯合成甲基叔丁基醚的催化剂、热力学、动力学。综述了合成ＭＴＢＥ的主要原料异丁烯的生产过程，并总结了甲醇、异丁醇和甲醇、叔丁醇合成ＭＴＢＥ的研究开发进展。参考文献１６篇。     

甲醇生产主精馏塔的模拟计算

对甲醇精馏主塔进行了模拟计算，并以一实际生产装置沿塔身的温度与浓度分布进行了验证。结果表明，水和甲醇的平均偏差为０．９％，微量杂质，不计丁基油，平均偏差为４９ｐｐｍ，温度平均偏差为２．９℃。说明本计算方法及采用的模型参数是可靠的，可用于工程计算。本文进一步指出，为降低废水中醇类含量，较理想的方法是选择合适的精甲醇与丁基油的采出量。     

甲醇羰基化制醋酸铱基催化剂的研究

摘要 醋酸是一种重要的化工原料，甲醇羰基化是目前生产醋酸的主要方法， 铱基催化剂是最有发展前景的甲醇羰基化反应制备醋酸的催化剂。介绍了铱基催化 剂体系的催化机理、速度影响因素，并与铑基催化剂进行了比较．     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。