摘要
六碳烯烃是重要的化工原料，应用于很多领域。丙烯二聚反应是制备六碳烯烃的重要方法，随着丙烯二聚催化剂研究的不断深入，镍系配合物均相催化剂以其具有的高催化活性和性能稳定性等优点广泛出现于丙烯二聚研究，并取得很好的催化效果。而具有可控的二聚异构体选择性、更易实现连续化生产的负载型催化剂一直是研究的重点和热点，开发新型的丙烯二聚负载型催化剂更具有挑战性。本文制备出镍系配合物催化剂和负载离子液体基-镍系配合物复合体系催化剂，分别应用于丙烯二聚反应性能研究，主要内容和研究结果如下：
1)镍系配合物催化剂和功能化离子液体的合成，负载离子液体基载体与负载离子液体基-镍系配合物复合体系催化剂的制备。通过红外光谱分析，结合熔点和元素分析的测试结果，确定了合成的四种镍系配合物（乙酰丙酮镍、双水杨醛镍、双[水杨醛(邻甲基苯)亚胺]镍和双[水杨醛(对硝基苯)亚胺]镍）的分子结构；通过两步合成法合成具有乙氧基团的功能化离子液体，利用红外、核磁共振测试手段分析了中间体和目标产物的化学结构；选择不同孔径的TS-1、MCM-41、SBA-15和硅胶四种表面富含羟基的载体材料，通过浸渍把功能化离子液体负载在这些载体材料上制备出负载离子液体基，红外和热重分析的结果表明离子液体以键合的方式负载在载体上；最后，采用浸渍法制备出离子液体基-镍系配合物复合体系催化剂。
2)系统研究了双[水杨醛(对硝基苯)亚胺]镍均相催化丙烯二聚的反应性能。结果表明：反应温度、压力和助催化剂用量都会对丙烯转化率、六碳烯烃中异构体的选择性和催化剂的TOF产生影响。适当增大反应压力和助催化剂的量可提高丙烯的转化率和催化剂的TOF，反应温度为常温、压力0.4MPa、Al/Ni的摩尔比为300可同时使丙烯转化率和催化剂的TOF达到较高的水平。适当提高反应压力、降低反应温度并增大助催化剂的用量可以提高二聚目的产物4-MP和2,3-DMB的选择性。
3)对比考察了其余三种镍系配合物催化剂均相催化丙烯二聚反应的性能。对照结果表明：四种镍配合物催化剂的反应性能较为接近，乙酰丙酮镍催化剂的TOF最低，使用具有强吸电子基团的双[水杨醛(对硝基苯)亚胺]镍催化剂，丙烯的转化率和催化剂的TOF更高，丙烯的转化率达到98.2%，TOF高达2.9×10~5h~(-1)。
4)考察了负载离子液体基-镍系配合物复合体系催化剂催化丙烯二聚的间歇反应性能，初步结果表明：与均相催化的丙烯二聚反应结果相比，使用负载离子液体基-镍系配合物复合体系催化剂，目标产物4-MP和2,3-DMB的选择性有了明显的提高，以ILMCM-41为载体时，4-MP和2,3-DMB的选择性能分别提高8.2%和10.0%；以ILSBA-15为载体时，可以把4-MP的选择性提高18.0%，证明负载离子液体基载体在丙烯二聚反应中起到了择形催化的作用。
Six carbon olefins are important chemical raw materials in many fields. One of the important sixcarbon olefins preparation methods is catalyzed dimerization of propylene. Within progresses of thecatalysis research for propylene dimerization, Ni-based complexes have been repeatly emerged in researchwork for propylene dimerization because of its excellent activity and stability. However, catalyst withcontrollable high selectivities for isomers and suitable continuous production performances has alwaysbeen the key target. So, developing novel supported catalysts for dimerization of propylene is becomingmore and more important. In this dissertation, four Ni-based complexes catalysts and some supported ionicliquid and Ni-based composite catalysts have been prepared.Both batch propylene dimerizationperformances of Ni-based complexes catalysts in homogeneous mode and supported ionic liquid andNi-based composite catalysts in heterogeneous were investigated, respectively. The main contents andconclusions are as follows:
Firstly, Ni-based complexes, functionalization ionic liquid, supported ionic liquid and supported ionicliquid-Ni-based complexes composite catalysts were synthesized. Among the four synthesized Ni-basedcomplexes of acetylacetone nickel, bis(salicylaldehyde) nickel, bis(salicylald(o-methylbenzene)iminate)nickel and bis(salicylald(p-nitrobenzene)iminate) nickel, chemical structures are proved by the infraredspectrometry detection and melting point determination and element analyses. Also, the chemical structureof intermediate and target functionalization ionic liquid synthesised by two step methods werecharacterized by means of Infrared(IR) Spectrometry and Nuclear Magnetic Resonance (NMR)Spectroscopy. Four supported materials such as TS-1, MCM-41, SBA-15and silica gel with different size pore and abundant hydroxide radicals on surface were selected to supported ionic liquid. InfraredSpectrometry and Thermo-gravimetry (TG) analyses results show that ionic liquid was covalent-anchoredon the support matrials surface. Then, supported ionic liquid and Ni-based coordination compoundscomplex catalysts were prepared by immersion method.
Moreover, performances using bis(p-nitrobenzene-N-salicylaldimine)-nickel complex as propylenedimerization catalyst have been investigated by semi-batch reaction. Results indicate that reactiontemperature, pressure and the amount of co-catalyst influence the conversion of propylene, selectivity forsix carbon olefins isomers and turnover frequency of catalyst. Propylene conversion and turnoverfrequency increase with the reaction pressure and the amount of co-catalyst added. The conversion rate ofpropylene and turnover frequency both attained ideal level simultaneously on conditions including ambienttemperature, pressure0.4MPa, and the molar ratio of Al/Ni300, respectively. The selectivities of targetisomer products could be improved providing increased amount of co-catalyst and reaction pressure on thesame time reduced reaction temperature.
Then, propylene dimerization performances of the other three kinds of catalysts of Ni-basedcomplexes were investigated comparisonly. Results show that selectivity of target product isomer andconversion of propylene have no obvious difference among the four Ni-based complexes catalysts. But theturnover frequency of acetylacetonate nickel cayalyst was the lowest one.Bis(p-nitrobenzene-N-salicylaldimine)nickel catalyst with electron withdrawing group could cause highersingle pass conversion and turnover frequency. The upmost conversion of propylene and turnoverfrequency of catalyst are98.2%and2.9×105in one of the propylene dimerization test.
Finally, supported ionic liquid and Ni-based composite catalysts was used to investigate the propylenedimerization performances in the heterogeneous semi-batch operation mode. Preliminary results show that supported ionic liquid-Ni-based complexes composite catalysts could improved the selectivity of4-methylpentene and2,3-dimethylbutene isomer distinctly. Using MCM-41as supporter, the increasedselectivity of4-methylpentene is8.2%and2,3-dimethylbutene10.0%with respect to homogeneouscatalysis. As to SBA-15as support, the net increased selectivity of4-methylpentene is18.0%. Thesewitness indicates that the MCM-41and SBA-15support materials play the so-called shape-selective rolesin the heterogeneous propylene dimerization catalysis processes.
引文
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