【作者】 陈波；

【导师】 何鸣元； 单永奎；

【作者基本信息】 华东师范大学 ， 分析化学， 2004， 博士

【摘要】 苯与长链烯烃烷基化反应制得的直链烷基苯、二苯醚与烯烃烷基化反应生成的烷基二苯醚是两类重要的工业反应中间体，它们经进一步的磺化、中和过程生产的烷基苯磺酸盐和烷基二苯醚磺酸盐是优良的阴离子表面活性剂，是现代合成洗涤剂工业产品中的主要成分。为适应当代环境保护的要求，化学工业必须走可持续发展之路，这就要求这两类工业烷基化反应采用新型的环境友好催化剂以取代传统的液体酸催化剂，同时提高产品的质量，增加可生物降解的直链烷基苯2位和3位异构体选择性，防止洗涤废液对环境造成污染。取代传统液体酸催化体系的途径，主要集中在催化剂的选择上，其中包括多种无机固体酸和有机固体酸，目前这些固体酸催化材料存在的主要缺点是反应选择性不高、反应条件苛刻以及催化剂失活等问题。 本论文工作选取了氧化锆固体超强酸、离子液体和负载杂多化合物三种类型的催化材料加以研究。考察制备过程中各种影响因素的作用，并对所制备的催化剂进行傅立叶变换红外光谱、差热-热重、比表面与孔径分布、X射线粉末衍射等表征，通过利用氨气吸附红外光谱、氨气吸附-程序升温脱附等手段研究了固体酸的酸性质；将所制备的新催化材料应用于苯／二苯醚的烷基化反应，研究反应过程中各种条件参数的影响，以期达到提高反应转化率和异构体产物的选择性、提升产品质量、优化反应条件，以及催化剂高效优质的研究目的。 研究的主要内容及基本结论如下： 1．氧化锆固体超强酸的制备与催化芳香族化合物与长链烯烃的烷基化反应研究，考察了锆源的选择、水解的温度、锆盐沉淀过程碱性物种的选择和滴加速度、碱化过程中的pH值、沉淀陈化的温度和时间、氯离子存在与否、酸促进剂的种类和浓度、酸处理氧化锆的方式和时间、煅烧温度和时间等合成条件对最终制备的样品的催化性能的影响，其结果证明pH值、氧化锆的晶型、酸促进剂的浓度和处理时间、煅烧的温度和时间是制备过程中的关键因素，对催化剂的活性起决定性作用。在苯与1-十二烯的烷基化反应中，以氧摘要化错固体超强酸作为催化剂，设定条件参数为苯与1一十二烯的摩尔比10，353K，常压下反应1小时可得最好的实验结果。反应转化率100%，产品直链度100%，2位与3位异构体选择性高于60%，并克服了固体超强酸一次使用完全失活的缺点;在二苯醚与1一十二烯的烷基化反应中，在醚烯摩尔比5，温度343K、常压的反应参数下反应2小时得最佳的实验结果，反应转化率到达了67%以上，产物为单取代烷基二苯醚单一产品，均优于目前使用的无水三氯化铝催化剂;2.离子液体催化苯、二苯醚与1一十二烯的烷基化反应，设计合成了胺盐类、咪 哇类阳离子与Aic卜一、Fea4-、PFe’、B凡‘、5042一、c几503一等阴离子两两组 合而成的催化体系，研究不同阴阳离子的摩尔配比对离子液体催化剂催化性 能的影响，得出在氯铝酸盐离子液体中，阴阳离子的摩尔比例为2的离子液 体具有低温高活性的特点。氯铝酸盐阴离子组成的离子液体催化剂可在室 温、常压条件下在1分钟内催化苯与1一十二烯的烷基化反应，原料中苯与 1一十二烯的摩尔比例为10，单取代产品的直链度达到100%，2、3位异构体 的选择性在60%以上，反应完毕后离子液体与反应体系自动分层，使分离过 程简单易行。在催化二苯醚与1一十三烯的烷基化反应实验中，最佳操作条件 为常压下323K反应2小时，反应转化率达到84%以上，单取代产物选择性 1《X)%。3.多金属含氧簇合物及负载多金属含氧簇合物催化苯、二苯醚与基化反应，合成具有结构的四种多金属含氧簇合物，1一十二烯的烷为了克服多金属含氧簇合物过低的比表面积的限制，通过考察多种类型的载体，确定了SBA一15这一类新型的厚壁介孔分子筛材料作为主要研究的载体，它具有水热稳定性高、孔径大小可调、比表面积大、长程有序的六角形孔道等特点。采用真空吸附的新型负载方法，将磷钨酸纳米粒子组装到SBA.15的孔道之内，实验证明当磷钨酸负载于这类载体材料上之后，其催化活性较未负载的磷钨酸本体有了较大提升，相比于传统的浸渍法负载，真空吸附法制备的催化剂磷钨酸与载体之间的相互作用更强，负载量更多、吸附更牢固。实验中考察了负载量、孔径大小等因素的影响，结果证明以7一8个纳米孔径的今华庆顺应才学麟士学世般戈摘要SBA-15分子筛负载质量百分比在10一20%内的催化剂性能最佳，在反应前不需要活化即能表现出很高的催化活性。对于苯与1一十二烯的烷基化反应，催化剂用量少，原料与催化剂摩尔比>2000。在考察了反应温度、时间以及原料中苯烯摩尔比等条件参数的基础上，得到最佳反应条件为:苯与1一十二烯摩尔比10，351K，常压下反应30分钟。以1一十二烯计算转化率100%，产品直链度100%，2、3位异构体选择性合计在57%以上。负载磷钨酸催化剂催化二苯醚与1一十二烯的烷基化反应的较适宜反应条件为343K常压下反应2小时，醚与烯的摩尔比为5。反应的转化率在70%以上，产物为单一的十二烷基二苯醚，选择性100%。 由上述结论可见，针对与芳香族化合物与长链?更多还原

【Abstract】 The reaction of benzene alkylation with long chain olefin and diphenyl ether (DPE) alkylation with olefin are two important industrial reactions. The reaction products, linear alkyl benzene (LAB) and alkyl diphenyl ether are the intermediate of linear alkyl benzyl sulfonate and alkyl diphenyl oxide sulfonate production. After sulfonation and neutralization, two kinds of good surface active agents (SAA) are synthesized, the 2, 3-LAB isomers can be biodegraded and have excellent washing power. It is the base of modern synthesis detergent industry. The traditional catalysts application to the alkylation reactions are sulfuric acid, hydrofluoric acid and aluminum chloride which are out of time of environmental protection for their toxicity and corrosion, and it is hard to separate catalysts from the products. Green chemistry are the way of sustainable development of chemical industry in the future. Many kinds of solid acidic catalytic materials, including zeolites, molecular sieves, solid super strong acid, polyoxometalates, ionic liquids and organic solid acids, etc were studied for the alkylation reactions. The major disadvantages of solid acid catalysts in nowadays research efforts are their low selectivity, short life time and hard reaction conditions.In this works, three types of catalytic materials were studied; they were SO42-/ZrO2 solid super strong acid, ionic liquids and supported polyoxometalates. Design, preparation and characterization of these catalysts and their application in reactions of aromatic compounds alkylation with long chain olefin were the object matter. The catalysts synthesis conditions were researched and these materials were characterized by FT-IR, TG-DTA, BET, TEM, Powder XRD NH3-FTIR and NH3-TPD. The reaction parameters, such as reaction temperature, pressure, volume of catalyst in use and mole ratio of reactants were investigated. Thereinafter the procedures and the conclusions were listed.1. In the process of SO42-/ZrO2 solid super strong acid synthesis, the pH value of precipitation, the concentration of H2SO4 and the calcine temperature and time determined the catalysts’ performance. The ZrCl4 should be precipitated in the range of pH 9-10, after the Zr(OH)4 were treated in 0.1-0.5mol L-1 H2SO4 solutions for 3-6 hours, they were calcined in 823-923K for 3-6 hours. Application in benzene alkylation with 1-dodecene, the conversion was 100%,the linearity of products was 100%, and the selectivity of 2-isomer was about 40%. The catalyst can be reused 5times. In the reaction of diphenyl ether alkylation with 1-dodecene, reaction conditions: DPE : 1-dodecene = 5, 343K, normal pressure, the conversion was above 67% and the selectivity of mono-alkyl diphenyl ether was 100%after 2 hours.2. Among different kinds of ionic liquids synthesized in this work, the AlCl3 type of ionic liquid show the highest catalytic activity when AlCl3 : cations = 2. The reaction of benzene alkylation with 1-dodecene can be completed in less than 1 min catalyzed by AlCl3 IL, room temperature, normal pressure, benzene ’. 1-dodecene = 10, the selectivity of 2 and 3 isomers was above 60%. The conversion of DPE alkylation with 1-dodecene was 84% after 2 hours at 323K, and the selectivity of mono alkyl diphenyl ether was 100%.3. As a new kind of mesoporous molecular sieves, SBA-15 shows the great characters of good supporter with thick wall, high hydrothermal stability, large specific surface. Preparation of PW/SBA-15 by a new vacuum method through supported tungstophosphoric acid (PW) on SBA-15, the catalyst has high catalytic performance in alkylation reactions. Reaction conditions: benzene : 1-dodecene = 10, 351K, normal pressure, 30min. The conversion of benzene alkylation with 1-dodecene was 100%, linearity wasl00%, the selectivity of 2-LAB nearly 40%, and the recycle times of catalyst reuse was 9. In reaction of DPE alkylation with 1-dodecene, the conversion was 100% after 2 hours, reaction temperature 343K, the mono alkyl DPE selectivity was 100%更多还原