邻硝基苯甲醛的成对电合成

本文研究了由同一电解池的阴极和阳极反应所产生的Ｃｅ~（４＋）和ＨＯ~·自由基将邻硝基甲苯氧化成邻硝基苯甲醛。阴阳极反应的邻硝基苯甲醛选择性大于９９％。最大的总电流效率达１６８％。讨论了影响阴极电流效率和总电流效率的因素。     

固定床电化学反应器研究(Ⅱ)硝基苯电化学还原制备对氨基苯酚

研究了在固定床电化学反应器内硝基苯电化学还原制备对氨基苯酚的过程.采用文献[7,8]建立的固定床电化学反应器模型对该反应过程进行了反应器设计.实验测得该反应的摩尔选择性β≥80%,电流效率η_i≥75%,反应器表观电流密度i≥1500A/m~2.本研究为固定床电化学反应器内硝基苯电化学还原制备对氨基苯酚过程工业化奠定了重要的理论基础.     

固定床电化学反应器研究(Ⅱ)硝基苯电化学还原制备对氨基苯酚

研究了在固定床电化学反应器内硝基苯电化学还原制备对氨基苯酚的过程.采用文献[7,8]建立的固定床电化学反应器模型对该反应过程进行了反应器设计.实验测得该反应的摩尔选择性β≥80%,电流效率η_i≥75%,反应器表观电流密度i≥1500A/m~2.本研究为固定床电化学反应器内硝基苯电化学还原制备对氨基苯酚过程工业化奠定了重要的理论基础.     

脂肪醇的胺化反应

本文对长链脂肪醇胺化反应的热力学和反应途径作分析，在此基础上研究了改进铜镍胺化催化剂选择性的方法，发现某些稀土元素有显著的抑制高沸物生成的作用，分析了催化剂失活的原因，新开发的铜镍／载体催经剂能够达到醇转化剂≥９９％，选择性≥９８％，叔胺收率≥９７％水平。     

二乙基羟胺的合成研究

本工作研究了以三乙胺、过氧化氢为原料,在催化剂存在下合成二乙基羟胺(DEHA)的主要影响因素。实验结果:三乙胺氧化反应的转化率≥99.5％,氧化三乙胺选择性接近 100％,以三乙胺计,DEHA全程收率≥96％;已可提供 33％和 85％两种 DEHA业产品,     

二元羧酸酐催化合成新工艺研究

采用催化脱水环化新工艺，对衣康酸和丁二酸等二元羧酸的脱水环化成酐反应过程进行了研究。开发了一种新颖的高活性、高选择性的YL型催化剂，考察了催化剂量、反应温度和原料配比等工艺条件对反应结果的影响，在较佳条件下，产品收率≥90％，产品纯度≥99％。     

混合丁烯剂聚催化剂及其工艺研究（下）

介绍了在Ｔ－９９新型固体磷酸催化剂作用下混合丁烯齐聚反应的研究。反应在空速３ｈ＾－１，超临界相态（对比压力Ｐｒ≥１，对比温度Ｔｒ≥１）－近临界相态（Ｐｒ≥１，Ｔｒ〈１）结合的条件下进行。反应温度从１８０℃提高到２３０℃，混合丁烯转化率由７５％上升到９４％，产物中二聚物异辛烯选择性ＳＣ８在７８％～９１％，十二烯选择性Ｓｃ１２在６％～１０％，Ｓｃ８与Ｓｃ１２之和达到９０％以上。     

草酸电解还原制乙醛酸反应中添加剂的结构

以铅电极上草酸电解还原合成乙醛酸的反应为研究对象,考察了电解合成添加剂的结构对反应的影响。结果表明,添加剂的阴离子对电流效率和反应选择性影响显著。阴离子基团越对称,最长的烷基链越短,则电流效率越高,反应选择性越好。     

丝光沸石催化剂对甲醇胺化反应性能的研究

制备了经阳离子改性的合成丝光沸石催化剂，并用于甲醇与氨选择性合成二甲胺反应。在200-400℃及0.5～3．5MPa范围内考察了工艺条件对该催化剂反应性能的影响。结果表明：该催化剂具有优良的转化活性和二甲胺选择性。在300-330℃，甲醇单程转化率≥98．5％．二甲胺单程选择性≥60％，该催化剂性能稳定、强度高，具有工业化价值。     

双极膜制酸制碱电流效率的测定

双极膜制酸碱的电流效率是反映双极膜性能的重要参数，它主要取决于双极膜阴，阳膜层对离子的选择性。本文设计了测试双极膜阴、阳膜层对离子的选择性和制酸制碱电流效率的简单、可靠方法，并用该方法完成了自制双极膜和上海产异相双极膜电流效率的测试实验。     

Electrocatalytic hydrogenation of phenol on dispersed Pt: Effect of metal electrochemically active surface area and electrode material

The influence of the electrochemically active surface area on the electrocatalytic activity for phenol hydrogenation has been investigated. It is shown that the current efficiency of the reaction does not change significantly for Pt loadings between 2% and 30% whereas a significant decrease in activity is observed for 60% Pt loading. This is used to classify this reaction in terms of its sensitivity. The influence of the electrode material and the alloying component on both current efficiency and on the reaction selectivity is determined. The material and the alloying component which exhibited the best efficiency and selectivity are deduced.     

2甲-基吡啶在丙酮-水混合溶剂中的电氧化

在质子交换膜为隔膜的电解槽内,以2甲-基吡啶为原料,在丙酮/水混合溶剂中,以PbO2为阳极,电氧化合成了2-吡啶甲酸。通过循环伏安、线性扫描伏安和恒电位电解实验,考察了丙酮与水体积比、反应温度、硫酸浓度、反应物2-甲基吡啶浓度和阳极电位对选择性和电流效率的影响。结果表明,V(丙酮)∶V(水)=3∶1,硫酸浓度1.0~1.2 mol/L,2甲-基吡啶浓度0.5 mol/L,温度30℃,阳极电位1.75~1.80 V,生成2吡-啶甲酸的选择性可达88.7%,电流效率达到48.3%。而在纯水作溶剂的溶液中,相同条件下生成2-吡啶甲酸的选择性和电流效率仅分别为67.4%和42.2%。     

ADJUSTMENT OF THE SELECTIVITY OF A DIELS-ALDER REACTION NETWORK USING SUPERCRITICAL FLUIDS

The thermodynamic pressure effect on rate constants is reported in supercritical fluid carbon dioxide for a homogeneous reaction network over a wide density range. The selectivity, or ratio of rate constants, has been controlled over a continuum for the parallel Diels-Alder additions of methyl acrylate and cyclopentadiene by adjusting the pressure at constant temperature. This reaction network is well-suited to provide fundamental insight into the nature of supercritical solvent effects since three simplifications arise: the pressure effect on the selectivity is independent of the partial molar volumes of the reactants, the temperature effect on the selectivity is independent of the partial molar enthalpies of the reactants, and the ratio of the endo- to exo-rate constants based on mole fraction units is the same as that based on concentration units. The selectivity for the more polar product, the endo-adduct, increases as the pressure or density increases, which indicates that it has a more negative partial molar volume in the transition state due in part to stronger induction forces. The slope of the logarithm of the selectivity is shown theoretically to increase as a function of the isothermal compressibility at constant temperature. At constant pressure, the selectivity decreases with temperature which indicates that the magnitude of the partial molar enthalpy is greater for the more polar endo-transition state than the exo-state. Solvatochromic polarity scales may be used to correlate quantitatively the solvent on this reaction network at supercritical fluid conditions.     

Studies on chemical activators for electrode I: Electrochemical activation of deactivating cathode for oxalic acid reduction

Electrosynthesis of glyoxylic acid by electroreduction of oxalic acid has long been well known. However, attempts to commercialize the process have encountered problems due to rapid deactivation of the cathode. The cathode activity can be continuously restored by adding small amounts of chemical activators to the catholyte. In this paper the structural effect of chemical activator on electrode reaction is studied. The results show that (1) It is the cation of the chemical activator, but not the anion that affects the current efficiency and the reaction selectivity. (2) The more symmetrical the cation, or the shorter the longest alkyl chain, the higher the current efficiency and the reaction selectivity become. (3) Mechanism of the activation is discussed. Adsorption of the cations of the activator on the cathode surface protects the electrode. (4) Quantitative characterization of the activator molecule is given using some topological indices, with which the activation ability can be predicted, and screening of the proper activator is made possible.     

十二烷基苯磺酸钠对2-甲基吡啶电氧化的影响

通过恒电位电解实验,在以质子交换膜为隔膜的电解槽内,将十二烷基苯磺酸钠(SDBS)添加于2-甲基吡啶电氧化的有机合成体系中,研究了2-甲基吡啶在PbO2电极上的电氧化行为。通过实验确定最佳条件为:2-甲基吡啶浓度为0.5mol·L-1,H2SO4浓度为1.0mol·L-1,丙酮/水(3∶1)为溶剂,阳极电位为1.8V,反应温度为30℃,SDBS浓度为1.6×10-3mol·L-1,电解理论电量的20%,其选择性为81.98%,电流效率为59.32%。在该实验环境下,SDBS对2-甲基吡啶电氧化有明显的促进作用,选择性和电流效率都有明显的提高。     

Electro-oxidation rate ofp-tert-butyltoluene in a bipolar packed-bed electrode cell

The side chain methoxylation ofp-tert-butyltoluene was carried out in a bipolar packed-bed electrode cell in which graphite pellets of diameter 4.74 mm and length 5mm were randomly packed in nine layers separated by inert mesh spacers. The reaction consisted of main consecutive reactions leading top-tert-butylbenzyl methyl ether andp-tert-butylbenzaldehyde dimethyl acetal (TBDA) and polymerization reactions. Overall reaction rate coefficients for each reaction step, current efficiency and energy consumption were determined on the basis of a reactor model. The selectivity and the current efficiency for TBDA increased with increasing current, but the energy consumption began to rise when the current exceeded 0.8 A. An addition of supporting electrolyte suppressed the overall reaction rate coefficients, although it decreased the energy consumption.     

卤族元素对Ag电极电催化还原CO2的影响

通过在电解液中加入卤族元素，系统地研究了卤族元素对于CO的选择性和反应速率的影响。结果表明，卤族元素对于CO₂的还原反应具有促进作用，并按照Cl^- < Br^- < I^-的顺序递增。Cl^-和Br^-对CO₂还原反应和析氢反应都具有催化作用，而I^-的存在加快了CO的生成，对析氢反应没有明显影响。在过电势为590 mV时，CO在有I-溶液中的选择性是无I^-溶液的28倍。经过表征和分析后得出，I^-具有较强的吸附性能，通过化学吸附使催化剂表面形貌发生改变，CO的活性位增多，加快其反应速率。同时，I^-在反应过程中易向反应表面传输负电荷，增加与碳原子的相互作用，从而提高CO的生成速率。     

固定床电化学反应器内电化学氧化法制备2,5-二甲氧基二氢呋喃

固定床电化学反应器内间接电化学氧化呋喃制备2,5－二甲氧基二氢呋喃的过程进行了研究,确定了电解条件及产品的分离与提纯工艺,研究表明,在操作温度为0－5℃的反应系统中,操作槽电压为4．0－6．0V,反应表观电流密度≥2000A／m^2,产品收率≥90％,电流效率≥90％,能耗（直流电）≤3．0kwh/kg产品。     

ANALYSIS OF THE PERFORMANCE OF NON-UNIFORMLY ACTIVE CATALYST PELLETS FOR A NON-ISOTHERMAL SERIES REACTION

An analysis of the influence of the non-uniform distribution of the active species in a catalyst pellet on the effectiveness factor and selectivity for the case of a series non-isothermal reaction is carried out. The case in which the desired reaction has a lower activation energy than the undesired reaction is considered. The effect of different reaction parameters on the selectivity for a single pellet is studied, and the optimum activity distribution is determined for high values of Thiele modulus. It is shown that temperature gradients within the pellet have a detrimental effect on local and overall selectivity and that these gradients are a strong function of the distribution of catalytically active material within the pellet.