氯铝酸室温离子液体介质中正碳十二烯选择环化反应

 在氯化1－丙基－3－甲基咪唑（PMImCl）、氯化1－丁基－3－甲\r\n基咪唑（BMImCl）、氯化1－丁基吡啶（BPCl）和溴化1－乙基吡啶（E\r\nPBr）季铵盐与AlCl3构成的室温离子液体介质中，首次发现正十二碳烯\r\n（简称十二烯）可以高选择性地发生环化反应生成环十二烷．依次在反\r\n应管中加入氯铝酸室温离子液体、乙醇和十二烯，其中AlCl3的量为0．\r\n01mol，AlCl3与季铵盐的摩尔比为2，乙醇为10ml，十二烯为2ml（9．\r\n3mmol）．当反应体系中不添加乙醇时，十二烯转化率和环十二烷选择\r\n性仅分别为4．2％和73．1％．这是由于十二烯和氯铝酸离子液体形成\r\n两相体系而不易充分接触，故十二烯转化率和环十二烷选择性较低．当\r\n反应体系中加入乙醇时，十二烯和氯铝酸离子液体体系变为单相，使得\r\n十二烯和氯铝酸离子液体可以充分接触，十二烯转化率和环十二烷选择\r\n性可分别达到12．4％和82．9％．压力对提高十二烯转化率和环十二烷\r\n选择性有很大的影响．p（N2）＝3．0～6．0MPa下反应12h，十二烯转\r\n化率和环十二烷选择性可分别达到27．2％和93．8％．反应结束后加热\r\n除去乙醇，产物自动与离子液体分层，便于分离，且离子液体介质可重\r\n复使用．     

铝交联皂石的合成和表征及催化性能

用XRD、化学分析、IR、MASNMR、TPD等手段表征了合成皂石及其铝交联物的结构。结果表明:皂石的交联密度与四面体层电荷和交联条件(Al/土比)有关。在乙醇氨化反应中,交联皂石显示了较好的催化活性和选择性。皂石的交联密度与液相产物分布的关系表明层柱材料对此反应具有择形催化作用。醇氨化反应可能是在吸附态NH_3和气相醇分子间进行的。     

乙醇羰化反应负载型催化剂的研究

本文由七种负载型催化剂中选出两种比较好的乙醇羰化催化剂,研究了影响反应转化率和选择性的因素,考察了活性组份的价态和载体的酸性。此外,还对催化剂进行了能量色散X射线分析。从其结果看,谱图上只有活性中心铑的谱峰而没有氯的谱峰,说明铑是以离子形式进入载体,而不是以化合物形式被吸附于载体上。     

合成气制乙醇的铑基催化剂中助剂铁,锂的作用本质研究

催化活性测试表明,助剂Fe具有显著提高乙醇生成选择性及铑催化活性的双重作用;助剂Li具有显著提高乙醇选择性的作用,对铑催化活性影响不大。基于H_2/D_2同位素效应结果及CO化学吸附、IR、XRD、XPS等的表征结果,认为助剂Fe经活化处理后大部分与Rh形成RhFe合金,使Rh分散度显著提高,从而提高了乙醇的选择性;Rh分散度的提高以及小部分以Fe~(2+)(Fe~(3+))形式存在的助剂Fe促进甲酰基的生成及随后的氢解断C-O键反应是助剂Fe促使铑催化活性提高的两个因素。Li的主要作用在于通过与C_2含氧中间体乙烯酮氧端的弱亲合作用,促进了乙醇前驱体的生成,从而使乙醇生成选择性提高。     

甲基丙烯酸—磷脂酰乙醇甲基丙烯酰胺共聚物LB膜的研究

制备了不同摩尔比的甲基丙烯酸-磷脂酰乙醇甲基丙烯酰胺共聚物,研究了这种共聚物在水面的表面压力(π)-分子面积(A)曲线、共聚物制成的MOS LB膜的电容(C)-电压(V)特性及此LB膜的相变温度。     

Excess enthalpies of solution of some primary and secondary alcohols in sodium dodecylsulfate micellar solutions

The exces enthalpies of solution of some primary and secondary alcohols in aqueous sodium dodecylsulfate micellar solutions were measured and the results were explained by considering the distribution of alcohols between aqueous and micellar phases. The distribution constant and the enthalpy of transfer (and the standard free energy and entropy of transfer) were obtained. The thermodynamic parameters for the transfer of secondary alcohols from the aqueous to the sodium dodecylsulfate (NaDS) micellar phase differ slightly from those of the corresponding primary alcohols. For both series of alcohols the additivity rule holds for free energies of transfer whereas enthalpies and entropies display convex curves. The present data are compared to those for the transfer of the same solutes from the aqueous to the dodecyldimethylamine oxide (DDAO) and dodecyltrimethylammonium bromide (DTAB) micellar phases. The role of the hydrophilic interactions between the OH group and the micelles' head groups is formulated. The thermodynamics of the branched methyl group were determined. Furthermore, the thermodynamics of solvation of primary alcohols in water, in NaDS micelles, and in octane have been calculated using reference states based on the assumption that the empty space around alcohols in the initial and final states is the same. It is shown that the solvation of alcohols in NaDS micellar phase is enthalpy driven and that the thermodynamic properties of solvation vs. the length of the alcohol tail is the same for water and NaDS micelles whereas it is different for octane. A possible explanation for this difference is that the alkyl chain of alcohols folds in octane.     

Biological production of ethanol from coal synthesis gas

The anaerobic bacteriaClostridium ljungdahlii produces ethanol and acetate from CO, CO₂, and H₂ in synthesis gas. Early studies with the bacterium showed that relatively high concentrations of ethanol could be produced by lowering the fermentation pH and eliminating yeast extract from the medium in favor of a defined medium. This article presents the results from a medium development study based on the aerobic bacteriumEscherichia coli. The results of continuous-reactor studies in a continuously stirred tank reactor (CSTR) with and without cell recycle are shown to demonstrate the utility of this improved medium.     

液—液萃取浮选法分离Ni（Ⅱ）,Co（Ⅱ）,Fe（Ⅲ）的研究

研究了在（ＮＨ４）２ＳＯ４存在下，乙醇与水分相的条件。试验表明，丁二酮肟与镍生成的螯合物沉淀可以被萃取浮选在乙醇与水两相之间，钴与丁二酮肟生成的螯合物被乙醇萃取，Ｆｅ（Ⅲ）留在水相中，实现了同一体系中三相分离Ｎｉ（Ⅱ），Ｃｏ（Ⅱ），Ｆｅ（Ⅲ），结果满意。     

碱金属沸石上乙醇双分子缩合反应及其机理

首次发现在碱金属Ｘ沸石上乙醇能够发生以正丁醇为主产物的双分子缩合反应，在所研究的催化剂中，含Ｒｂ的ＬｉＸ沸石表现出较高的反应活性和选择性。反应机理的研究表明，反应不经过ａｌｄｏｌ缩合步骤。在此基础上，对反应机理提出了新建议：在碱性沸石作用下，乙醇的β－位Ｃ－Ｈ键被活化，双分子脱水导致缩合。碳链的增长按此模式进行。     

Thermodynamic characteristics of solvation of individual ions in ethanol at −50 to 55°C

Experimentally determined are the enthalpies of solution of 12 electrolytes (LiBr, LiI, NaBr, NaI, NaBPh₄, Et₄NCl, Et₄NBr, Pr₄Br, Bu₄NBr, Am₄NBr, Ph₄PCl, Ph₄PBr) in ethanol at –50 to 55°C. _sH^o values obtained on the basis of four different extrapolation equations are analyzed. The effect of temperature changes on the thermodynamic parameters of solvation indindividual ions are calculated using thermodynamic data for the salt crystals (lattice) with the assumption that _solvC _p ^o (Ph₄P⁺)=_solvC _p ^o (Ph₄P^-).