【作者】 宋芬；

【导师】 李瑞丰；

【作者基本信息】 太原理工大学 ， 化学工艺， 2002， 硕士

【摘要】 本论文主要考察了用苯酐—尿素路线将MPc固定于Y型沸石分子筛中的可行性和不对称取代的金属酞菁络合物的合成及其封装到分子筛而制得的复合材料对环己烷的催化氧化性能。 1、本文首次采用苯酐—尿素路线，经由原位合成法将金属酞菁络合物MPc固定于Y型沸石中，并用XRD、FTIR、DRS、TG-DTA等手段对其进行了表征。结果表明MPc已被成功地固定于Y型沸石中及此制备路线的可行性。此外，对采用此制备路线制备MPc／Y时的各种影响因素进行了较为详细的探讨。结果表明：（1） 中心金属离子以Mn²⁺最佳，Co²⁺次之、Fe²⁺较差；随着中心金属离子含量的增加，样品对环己烷的转化率增大，但转化数下降。（2）采用本路线制备CoPcY的最佳条件为：a、采用氯化钴作为待交换的金属盐；b、络合温度以180℃为宜；c、起始反应物为苯酐、尿素、氯化铵、氯化铝、CoY时，制备出的CoPcY的催化性能最好； 2、首次采用苯酐和四溴苯酐均相浓缩统计合成法制得了不对称取代的金属钴酞菁络合物（CoPcBr_x），并采用¹HNMR、FTIR、DRS等对其进行了结构表征；此外，采用沸石合成法将其固定于MCM-41中孔分子筛，并对其催化性能进行了考察。结果表明：封装到MCM-41内的不对称溴取代的钴酞菁络合物CoPcBr_x对环己烷的氧化活性远高于封装到MCM-41内的对称溴取代的钴酞菁络合物CoPcBr₁₆和未被取代的钴酞菁络合物CoPc。 3、此外，本文还采用沸石合成法将不对称取代的钴酞菁络合物（CoPcBr_x）固定于Y型沸石而制得了CoPcBr_x／Y，考察了各种反应条件（反应温度、反应时间、反应介质、环己烷与过氧化氢的体积比及催化剂用量）对其氧化环己烷过程的影响。结果表明:（a）反应温度的影响:随着反应温度的提高，环己烷的转化率增大;（b）催化剂浓度的影响:环己烷的转化率随催化剂浓度的加大而增大;（c）反应体系的溶剂以乙酸最佳，乙睛最差;（d）环己烷/HZO:比的影响:随着HZOZ用量的增加，环己烷转化率和反应产物中环己酮和环己醇比逐渐增大;（e）催化剂寿命的考察:通过三次循环测试表明经过三次循环反应，催化剂的整体活性没有显著地降低。（f）反应时间的影响:无论室温氧化还是60℃下氧化环己烷，随着反应时间的延长，环己酮在产物中的比例呈增加趋势。更多还原

【Abstract】 This thesis mainly investigated the feasibility of encapsulation of MPc into the supercages of zeolite Y and the synthesis of unsymmetrical phthalocyanine and its immobilization in MCM-41 and zeolite Y . The catalytic performance of all samples was tested by cyclohexane oxidation as a model reaction.1 , It will be reported of the synthesis of metal phthalocyanine into the supercages of zeolite Y using Phthalic anhydride-Urea route via "ship-in-the-bottle" method , and its characterization by XRIX FT-IR> DRS, TG-DTA etc. The results showed that the synthesis route was feasible and metal phthalocyanine was successfully encapsulated into zeolite Y . The factors affacting the preparation of MPcY were investigated, too .The results manifested that (1) the center ion of Mn2+ was better than Co2+ and Fe 2+ . With increasing the content of the center ion in samples , the cyclohexane conversion increases, but the turnover number (TON) decreases .(2) the optimum reaction condition for preparation of CoPcY is as follows: a , using CoCl2 as the exchanged salt ; b , complexation temperature of 180 ; c . complexation catalyst of NH4C1 and A1C13 .2, The unsymmetrically substituted cobalt phthalocyanine complexes (CoPcBrx) were synthesized by statistical condensation of phthalic anhydride and tetrabromophthalic anhydride, and further immobilized in MCM-41 molecular sieves by zeolite synthesis method, as well as characterized by XRD,FT-IR,DRS, 1HNMRetc. The catalytic property of CoPcBrx/MCM-41was tested by cyclohexane oxidation using H2O2 or t-BOOH as oxidant. The catalytic results showed that the catalytic activity of CoPcBrx/MCM-41 was higher than that of CoPc/MCM-41 and CoPcBri6/MCM-41.3, CoPcBrx Y was prepared by zeolite synthesis method. Moreover , the influences of the factors, e.g. reaction temperature , reaction time , reaction medium , catalyst concentration and the volume ratio of cyclohexane to H2O2, on the catalytic performance in cyclohexane oxidation were also explored. The catalyst results showed : a , With increasing the reaction temperature, the cyclohexane conversion increases . b , in the catalyst concentration, the cyclohexane conversion also enhances, c , acetic acid is the best reaction medium , while acetonitrile was the worst . d , With increasing the amount of H2O2 in reaction system , the higher cyclohexane conversion and the ratio of cyclohexanone to cyclohenanol are obtained . e ,With increasing the reaction time , the conversion of cyclohexane increased and the yeild of cyclohexanone also improves . Moreover , the catalytic activity of the catalyst remains the same after three recycles of reaction under the identical condtion.更多还原