【作者】 徐晓清；

【导师】 吕连海； 荣泽明；

【作者基本信息】 大连理工大学 ， 应用化学， 2011， 硕士

【摘要】 环己烷二甲酸二甲酯是一类重要的有机中间体,广泛地应用于香精、化妆品及聚合物的改性剂。目前,人们对于苯二甲酸二甲酯催化加氢制备环己烷二甲酸二甲酯进行了大量的研究,工业生产多采用贵金属催化剂,但普遍存在着反应条件苛刻、催化剂成本较高、选择性较差、贵金属活性组分流失等缺点。因此,开发新型高效催化剂用于苯二甲酸二甲酯加氢反应中,具有重要的理论研究及实际应用意义。本文采用骤冷法制备改性骨架镍(QS-Ni),以邻、间、对苯二甲酸二甲酯催化加氢为探针反应,系统考察了反应参数对加氢反应的影响,并在最优工艺条件下测试催化剂的稳定性。实验结果表明,QS-Ni展现了优异的催化活性和稳定性,目标产物选择性高,纯度好,具有潜在的工业应用价值。将QS-Ni应用于邻苯二甲酸二甲酯(DMP)选择加氢制备1,2-环己烷二甲酸二甲酯的反应中,以异丙醇作溶剂、反应温度100℃、氢气压力4.0MPa、底物初始浓度2.7mol/L、原料与催化剂质量比20：1条件下,DMP转化率100%,目标产物选择性为99.3%。在此条件下,催化剂连续循环套用10次,仍保持较高的活性和选择性。将QS-Ni应用于对苯二甲酸二甲酯(DMT)催化加氢制备1,4-环己烷二甲酸二甲酯(DMCD)反应中,异丙醇为溶剂,DMT初始浓度为1.Omol/L,原料与催化剂质量比4:1,在95℃和6MPa条件下反应140min,DMT转化率为100%,DMCD选择性达92.3%。在相同的反应条件下,催化剂循环使用16釜后,原料转化率在99.3%以上,DMCD选择性为92.0%。将QS-Ni应用于间苯二甲酸二甲酯(DMIP)催化加氢制备1,3-环己烷二甲酸二甲酯反应中,选用异丙醇做溶剂,反应温度90℃,氢气压力5.0MPa,原料转化100%,产物选择性达94.3%。更多还原

【Abstract】 Dimethyl cyclohexanedicarboxylates are important intermediates in organic synthesis, which are widely used in the preparation of fragrance, flavor or serve as a modifier of polymer. By now, researchers have done many investigations about the hydrogenation of dimethyl phthalate to dimethyl cyclohexanedicarboxylate. In order to reduce catalyst cost and loss of noble metal, it is urgent to develop more efficient, inexpensive catalyst to replace the noble metal catalyst.The Mo modified skeletal Ni catalyst (QS-Ni) was prepared by quenching technique, and it was employed for the catalytic hydrogenation of dimethyl phthalate (DMP), dimethyl isophthalate (DMIP) and dimethyl terephthalate (DMT). Effects of solvent, reaction temperature, H2 pressure, initial concentration of substrate and amount of catalyst have been investigated. Under optimal reaction conditions, the stability of QS-Ni has been tested. The catalyst showed excellent catalytic activity and high selectivity to desired product.QS-Ni was proved to be very active for the hydrogenation of DMP to dimethyl 1,2-cyclohexanedicarboxylate. Under optimal reaction conditions:c(DMP) =2.7mol/L, m(DMP):m(QS-Ni)=20:1,100℃,4.0MPa H2 pressure, the selectivity was up to 99.3% with 100% conversion of DMP in isopropanol solvent. The catalyst still exhibited excellent activity and selectivity after QS-Ni was recycled for 10 times.The modified skeletal Ni was proved to be also active for the hydrogenation of DMT to dimethyl 1,4-cyclohexanedicarboxylate (DMCD). Under optimal reaction conditions: c(DMT)=1.0mol/L, m(DMT):m(QS-Ni)=4:1,95℃,6.0MPa H2 pressure, the selectivity of DMCD was up to 92.3% in 140min with 100% conversion of DMT in isopropanol solvent. After QS-Ni catalyst was recycled for 16 times, conversion of DMT and selectivity to DMCD still remain at 99.3% and 92.0%, respectively.We also investigated the catalytic hydrogenation of DMIP to dimethyl 1,3-cyclohexanedicarboxylate over QS-Ni. The product selectivity was up to 94.3% with 100% conversion of DMIP under 90℃,5.0MPa H2 pressure in isopropanol solvent.更多还原