离子交换树脂催化剂的研究进展

离子交换树脂催化剂的研究进展摘要：本文介绍了离子交换树脂催化剂的结构，研究进展状况以及应用实例关键字：离子交换树脂催化剂结构研究进展应用实例Ion Exchange Resin Catalysts Were Reviewed Abstract：this paper introduces the structure of the ion exchange resin catalyst, research progress and application exampleKey word: ion exchange resin catalyst structure research progress on the application example离子交换树脂具有许多优点，如在水溶性酸作催化剂的情况下，会遇到设备腐蚀、副反应多、产品质量差、后续分离困难以及污染等问题，而使用离子交换树脂则可避免这些问题，可以大大简化后续的分离操作工序，而催化剂还可以重复使用。

当然，离子交换树脂的耐温性和耐磨性不太好，价格比较昂贵是其缺点[1]。

阳离子交换树脂是一类重要的固体酸催化剂, 用其取代传统的液体酸催化剂（如H2SO4、HF等）, 可以克服液体酸催化剂所存在的设备腐蚀、废水排放及副反应等问题。

与其它的固体酸材料相比, 离子交换树脂亦具有酸量高、机械强度高等优点[2]。

七十年代以来,国外在离子交换树脂催化剂的开发、应用方面取得了较大的进展,许多具有特定用途的具有特定的孔结构以及酸特性的树脂催化剂已经商品化, 运用离子交换树脂作为催化剂的一些具有较高经济效益的工业生产过程也已经开发了出来。

国内一些单位在这方面也做了许多的研究工作。

近年来，有很多人在进行离子交换树脂催化剂的改性研究。

下面，我们就来了解离子交换树脂的结构和最近的研究工作以及一些应用实例[3]。

1.离子交换树脂的结构普通的离子交换树脂是交联了二乙烯基苯的聚苯乙烯树脂。

通过调节二乙烯的含量，可以调节此类树脂的三维网络结构，这样制得的树脂称为凝胶型共聚物。

而大网络树脂可以通过苯乙烯和二乙烯基苯的共聚制得，具有较大的比表面积。

在共聚物中引入不同的官能团即可制得阳离子树脂和阴离子树脂。

如使用硫酸将共聚物中的苯环磺化即可制得强酸型阳离子树脂，而引入羧基则制得弱酸性阳离子树脂。

对于强碱性离子树脂则可通过在共聚物中引入季铵基而制得[4]。

2.离子交换树脂催化剂的研究进展2.1. 离子交换树脂支载的加氢催化剂的制备常州大学江苏省精细石油化工重点实验室的丁丽娟、何明阳等在“离子交换树脂支载的加氢催化剂的制备”中制备了一种离子交换树脂支载的Ni-B 非晶态合金催化剂，对催化剂形态及孔结构等进行了表征[5]；将该催化剂用于催化加氢法降低乙二醇中甲醛含量的实验，考察了反应温度、乙二醇空速和压力对该催化剂催化条件下甲醛去除率的影响[6]。

结果表明，Ni-B 分散在树脂载体表面和内部的孔中，催化剂孔径约20nm，属于介孔范围[7]；在反应温度353K、乙二醇液时空速3h-1、压力0.5MPa 条件下，催化剂连续运行500h，乙二醇中甲醛含量由45μg/g 降低至3μg/g以下，甲醛去除率达到95% [8]。

2.2. 负载Al 离子交换树脂固体催化剂的制备与应用研究华南理工大学轻工与食品学院的李妍、宁正祥研究制备了负载Al 的离子交换树脂催化剂, 并对制备条件进行讨论, 得到了较好的制备工艺为AlCl3与树脂的配比为8 %, 溶剂无水乙醇用量为80 mL, 78. 3 ℃回流反应8 h, 最终铝含量为1. 44 g/ 100 g 树脂[9]。

通过红外光谱对其进行表征, 结果表明732 树脂在1020 cm- 1处的吸收峰发生明显裂分, 形成1011 cm- 1和1025 cm- 1两个吸收峰, 说明732 树脂磺酸基与AlCl3发生了络合反应, 同时将其应用于丁烯二酸糠醇甲酯合成反应中取得了良好的催化效果[10]。

2.3. Pd/离子交换树脂催化剂的制备及加氢性能湖北省化学研究所的郑卡莉、张曼征用各种离子交换树脂为载休制备的载把催化剂可用于对不饱和化合物的常温常压加氢。

其加氢活性既与载体功能基的性质有关也与载体的物理特性有关[11]。

其中以孔度大、表面粗糙的树脂作载体利于底物与氢的扩散, 加氢活性高。

载体功能基要求与把有一定的配位能力, 同一功能基的配位原子数最好≤2。

催化剂活性中心的价态对加氢活性也有影响, 两种以上价态的把比例适当协同作用时活性高[12]。

负载型树脂催化剂兼具均相, 多相催化剂的高活性, 高选择性和易分离回收, 不污染产物的优点。

商品化的离子交换树脂有功能基, 并具有适当的孔度。

用做载体制备催化剂原料易得,制备简便[13]。

2.4.离子交换树脂支载的镍、钴、铜金属硼化物催化剂的研究硼氢阴离子交换树脂是一种聚合物还原剂, 已被使用到还原碳基、酞卤等功能基化合物[14], 而且在过渡金属盐作用下能够还原碳碳双键、硝基等功能基化合物[15]。

湖北大学化学系的覃彩芹、陈家威在“离子交换树脂支载的镍、钴、铜金属硼化物催化剂的研究”中报道用BER与氯化铜、氯化镍和氯化钻反应先制备聚合物支载的催化剂, 并探讨其催化作用。

然后研究其催化硼氢化钠对一些有机功能基化合物的还原作用[16]。

2.5.强酸型离子交换树脂支载的过渡金属催化剂过渡金属对有机化学反应有很好的催化作用[17],. 随着聚合物支载试剂的出现, 对于高分子催化剂的研究十分活跃[18]聚合物支载的过渡金属催化剂具有较高的催化活性和稳定性,易于分离和重复使用等优点[19]。

湖北大学化学系的陈家威和黄锦霞进行“强酸型离子交换树脂支载的过渡金属催化剂”的研究将Co2+、Cu2+、Ni2+等过渡金属离子接于强酸型离子交换树脂上, 比较了这九种聚合物支载催化剂对醇和烯醚加成反应的影响。

得出结论强酸型离子交换树脂支载的过渡金属催化剂制备简便, 对醇与烯醚的加成反应催化效果良好[20]。

3.离子交换树脂的催化应用实例3.1.醇与烯烃的醚化反应甲醇与异丁烯、乙醇与异丁烯、甲醇与2-甲基-1-丙烯可由酸性阳离子树脂催化醚化合成MTBE（甲基叔丁基醚）、ETBE（乙基叔丁基醚）和TAME（新戊基甲基醚）。

这些都可以作为汽车内燃机用汽油的辛烷值增高剂。

大孔磺酸树脂已用于大规模生产MTBE。

3.2.酯化反应酯化反应常用硫酸作催化剂，这往往造成副反应多、设备腐蚀严重、后续分离繁杂、废液污染环境等问题。

而使用离子交换树脂就可以很好的解决以上问题。

如马来酸二甲酯、马来酸二乙酯及马来酸二丁酯是生产聚合物的乳液、热塑性及热固性塑料的重要原料，它们可以由顺酐与甲醇、乙醇和丁醇酯化而得到。

顺酐与乙醇在酸性离子交换树脂的催化下，酯化产率很高，已由Rohm&Hass公司和BASF公司实现工业化。

3.3.烷基化反应Nafion、Amberlyst-15树脂可以催化苯与长链烯烃的烷基化反应，在80℃时，可以达到99%以上。

除烯烃作烷基化试剂以外，醇、卤代烃也可以进行烷基化反应。

Harmer等用离子交换树脂作催化剂对苯、对二甲苯与苯甲醇的烷基化反应做了研究，结果显示Nafion的活性比Amberlyst-15高。

其他的如具有广泛商业用途的烷基化反应也可以使用离子交换树脂作催化剂[21]。

4.结语近年来, 由于传统催化剂浓硫酸对设备腐蚀严重, 而且存在副反应多并产生大量废酸污染环境等缺点。

为适应绿色合成的需要, 人们正在不断开发新的无毒无害的催化剂来改进化工工艺。

固体酸催化剂是目前的开发热点, 离子交换树脂是其中研究较多的一类。

离子交换树脂具有许多优点，如在水溶性酸作催化剂的情况下，会遇到设备腐蚀、副反应多、产品质量差、后续分离困难以及污染等问题，而使用离子交换树脂则可避免这些问题，可以大大简化后续的分离操作工序，而催化剂还可以重复使用。

当然，离子交换树脂的耐温性和耐磨性不太好，价格比较昂贵是其缺点。

但近年来，对离子交换树脂催化剂的研究取得的成绩是显著的，离子交换树脂催化剂的研究发展也是光明的。

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Cationic ion exchange resins as catalystAbstractThis paper presents a review of the literature pertaining to catalysis by cation exchange resins. Emphasis has been given to the literature that has appeared during the last seven years. A variety of reactions catalyzed by cation exchange resins have been tabulated according to their broad classification; industrially important reactions have been delineated. Examples, where the use ofion exchange resin catalysis has led to an improvement in the selectivity of the desired products, have also been discussed. Approaches for the interpretation of kinetic data and modeling have been reviewed.The type of reactor to be employed for carrying out ion exchange resin catalyzed reactions has been discussed. A new emerging area is the adoption of distillation column reactors (e.g., methyl tert-butyl ether from isobutylene and methanol).Some aspects of the deactivation and regeneration of these catalysts have been briefly discussed. The use of ion exchange resins for the removal of impurities from mixtures and the separation of close-boiling compounds by exploiting their different chemical reactivity has been highlighted. Suggestions have been made for further work.6.Catalytic oxidation of trans-stilbene using pyrolysed manganese-loaded cation exchange resinAbstractThe work presented in this paper describes a method for the preparation of supported metal catalysts on carbon matrix. Manganese used as metal catalyst was loaded onto an ion exchange resin and this precursor was calcined over a wide range of temperature between 600 and 900 °C. The final materials consist of discrete (typically 0.5–0.8 mm diameter) spherical particles of manganese-loaded carbon. Electron microscopy was performed, which demonstrated that the structural integrity of the particles is maintained after calcination. Textural characterisation evidenced a correlation between the temperature of calcination, the specific surface area and the density of the calcined materials. The chemical moieties present, as found by XRD analysis, have been established and the catalytic activity of the material for oxidation reactions has been tested. The catalytic activity of the calcined materials was examined in the case of the oxidation of trans-stilbene to trans-stilbene oxide for different calcination temperatures. trans-Stilbene oxide and benzaldeyde were found to be the major products of the oxidation reaction. Conversions of >50%, at all pyrolysis temperatures, were achieved at 55 °C in 144 h.8.Improved and selective platinum recovery from spent α-alumina supported catalysts usingpretreated anionic ion exchange resinAbstractImproved and selective recovery of platinum from a spent dehydrogenation platinum α-alumina supported catalyst using a strong basic ion exchange resin is reported. Platinum and other precious metal group (PMG) complexes are leached using concentrated hydrochloric acid along with about 0.20 vol.% nitric acid as an oxidizing agent from de-coked and crushed spent catalyst. Effects of hydrochloric acid concentration, time, and temperature in leaching stage are investigated. The strong basic anionic resin is treated by sodium hydroxide solution to replace chloride anion by hydroxyl group ion. The supernatant of the leaching process is passed through a fixed column of hydroxylated strong base anionic resin. The treated resin on which the platinum complex is adsorbed is dried and burned in an oxidizing atmosphere at 750–800 °C. The recovered gray metallic powder is mainly platinum. Results compared with those obtained from untreated anionic resin show that adsorption of platinum complexes onto the treated anionic resin is more selective and the yield of separation is considerably improved. The breakthrough curves of the pretreatedanion exchanger and that of untreated exchange resin reveals that the capacity of the hyroxilated resin is decreased by about 14%. These breakthrough curves can be used for calculation of height of a practical exchange plate (HPEP) for design purposes.12. Transesterification of cyclohexyl acrylate with n-butanol and 2-ethylhexanol: acid-treatedclay, ion exchange resins and tetrabutyl titanate as catalystsAbstractTransesterification of cyclohexyl acrylate with n-butanol and 2-ethylhexanol was studied in a batch reactor using an acid-treated clay, ion exchange resins and tetrabutyl titanate as catalysts. The effect of various parameters on the conversion of cyclohexyl acrylate and towards the selectivity of cyclohexanol were studied to optimise the reaction conditions. The transesterified esters (n-butyl acrylate and 2-ethylhexyl acrylate) were separated from the reaction mixture by fractional vacuum distillation and were characterised by 1H NMR. The experimental results were described by a kinetic model based on Langmuir–Hinshelhood–Hougen–Watson (LHHW) mechanism for the transesterification of cyclohexyl acrylate with n-butanol in the presence of Engelhard F-24 as catalyst and the kinetic parameters were evaluated.14. Solid acid catalysis using ion-exchange resinsAbstractIn this review article, we describe the use of commercially available polymeric ion-exchange resins for a range of industrially important transformations. Recent developments both on the materials design and applications will be described. Examples of high catalytic activity will be described in areas ranging from alkylation, transalkylation, isomerization, oligomerization, acylation, esterification and nitration. The two main classes of ion-exchange resins are based upon styrene-based sulfonic acids (Amberlyst® and Dow type resins), which show very high activity in the areas of esterification and etherification, to the perfluorosulfonic acid-based catalysts including the recently developed Nafion® resin/silica nanocomposites. These show very high activity in the area of linear alkyl benzene formation, isomerization, and some select acylation type chemistries. These new types of catalysts (which have been used commercially) are adding to the ever-growing portfolio of highly active solid acid catalysts, which couple both economic and environmental drivers to improve organic transformations within the chemical industry.。