【作者】 许建华；

【导师】 黎先财；

【作者基本信息】 南昌大学 ， 无机化学， 2007， 硕士

【摘要】 环境友好与绿色化生产技术是当前催化研究与开发的前沿，其主要的研究内容之一就是重新考虑、改造和设计石油化工生产企业仍大量沿用着的三废高和环境污染严重的传统反应工艺。目前，己二酸的主要生产方法为环己醇和环己酮为原料的硝酸氧化法，虽然其己二酸收率（92％-96％）较高，但存在设备腐蚀严重等缺点，尤其是生产1t己二酸产品消耗68％的硝酸1.3t，产生的N₂O，NO_x，以及废酸液造成了严重的环境污染问题。因此，研究与开发清洁催化氧化合成己二酸的方法已成为化学工业领域中的一个重要课题。本文结合我省钨资源优势，寻找出新型钨催化剂，并用于催化合成己二酸、乙酸正丁酯。在常压、无有机溶剂和相转移催化剂情况下，以30％H₂O₂为氧源，以WO₃为催化剂，用H₂O₂氧化环己醇合成己二酸。探讨了催化剂用量、H₂O₂用量、反应温度和时间等条件对反应的影响。在优化工艺[n（环己醇）∶n（H₂O₂）∶n（WO₃）=100∶600∶4]条件下，反应温度为100℃，反应时间6h，己二酸分离收率可达67.6％，纯度为99.8％；催化剂重复使用5次后，己二酸收率仍可达60.2％。以（NH₄）₅[H₂（WO₄）₆]·H₂O为催化剂，用H₂O₂氧化环己醇合成己二酸。探讨了催化剂用量、H₂O₂用量、反应温度和时间等条件对反应的影响。在优化工艺[n（环己醇）∶n（H₂O₂）∶n（钨酸铵）=100∶550∶1，反应温度为90℃，反应时间6h]条件下，己二酸分离收率可达78.4％，纯度为99.8％。催化剂重复使用3次，己二酸收率稳定。以（NH₄）₅[H₂（WO₄）₆]·H₂O为催化剂，用H₂O₂氧化环己酮合成己二酸。探讨了催化剂用量、H₂O₂用量、反应温度和时间等条件对反应的影响。在优化工艺[n（环己酮）∶n（H₂O₂）∶n（钨酸铵）=100∶400∶0.5，反应温度为90℃，反应时间5h]条件下，己二酸分离收率可达80.9％，纯度为99.8％。催化剂重复使用4次，己二酸收率95.8％（纯度74.3％）。本实验发现用（NH₄）₅[H₂（WO₄）₆]·H₂O催化合成己二酸的收率比用WO₃催化合成己二酸的收率更高，同时发现用H₂O₂氧化环己酮合成己二酸的收率比用H₂O₂氧化环己醇合成己二酸的收率更高；所以可以得出结论：用钨酸铵催化H₂O₂氧化环己酮这一工艺具有己二酸收率高、催化剂用量少、H₂O₂利用率高、反应温度低、反应时间短、催化剂的重复使用性能较好等优点。通过水热法制备出SO₄^2-／ZrO₂固体酸催化剂，对催化剂进行XRD、IR表征，并以冰乙酸和正丁醇的酯化反应为探针，探讨了各个因素对反应的影响。结果表明，当反应时间为2h，n（正丁醇）∶n（冰乙酸）=2∶1，催化剂用量为0.2％（占总物料的质量分数），酯化率可达99.1％。更多还原

【Abstract】 An environmentally benign and green process is highly desirable in the development of catalysis. One of the most important fields is to rebuild the conventional processes of petrochemical production, which measurably contribute to pollution. Currently, the industrial production of adipic acid still uses the oxidation of cyclohexanol/cyclohexanone mixture with nitric acid. The yield and selectivity are both high, but erosion is severe. Besides, the emission of N₂O、NO and the waste acid damage environment remarkably. Therefore, the development of the clean process for the adipic acid is an important subject in the chemical industries.In this work, tungsten resource with ample supply in China especially in Jiangxi province was used as catalysts in the green synthesis of adipic acid, n-butyl acetate. And we mainly carried out the following aspects of research works as follows:Adipic acid was synthesized by WO₃ catalyzed oxidation of cyclohexanol with 30% hydrogen peroxide. The influence of reaction conditions such as catalyst amount, hydrogen peroxide amount, reaction temperature and time on the oxidation was investigated. Under the optimal conditions, i. e. when n （cyclohexanol） : n（hydrogen peroxide） : n （tungsten trioxide） was 100 : 600 : 4, and the reaction temperature was 100℃, the reaction time was 6 h, the isolated yield of adipic acid could reach 67.6% and its purity was 99.8%. The catalyst could be reused for 5 times and the isolated yield of adipic acid was still above 60.2%.Adipic acid was synthesized by ammonium tungstate catalyzed oxidation of cyclohexanol with 30% hydrogen peroxide. The influence of reaction conditions such as catalyst amount, hydrogen peroxide amount, reaction temperature and time on the oxidation was investigated. Under the optimal conditions, i. e. when n （cyclohexanol） : n （hydrogen peroxide） : n （ammonium tungstate） was 100 : 550 : 1, and the reaction temperature, was 90℃, the reaction time was 6 h, the isolated yield of adipic acid could reach 78.4% and its purity was 99.8%. The catalyst could be reused for 3 times and the isolated yield of adipic acid was still stable. Adipic acid was synthesized by ammonium tungstate catalyzed oxidation of cyclohexanone with 30% hydrogen peroxide. The influence of reaction conditions such as catalyst amount, hydrogen peroxide amount, reaction temperature and time on the oxidation was investigated. Under the optimal conditions, i. e. when n （cyclohexanone） :n （hydrogen peroxide） :n （ammonium tungstate） was 100 : 400 : 0.5, and the reaction temperature was 90℃, the reaction time was 5 h, the isolated yield of adipic acid could reach 80.9% and its purity was 99.8%. The catalyst could be reused for 4 times and the isolated yield of adipic acid was 95.8% and its purity was 74.3%.In this dissertation, we found that the catalyst, ammonium tungstate, could be reused for many times and the isolated yield of adipic acid was still high. This work was different from the predecendent works in that the used catalyst was simplier, cleaner and more efficient. And the activity of the catalyst would be better, the amount of hydrogen peroxide was little, the reaction temperature was low, the amount of reaction time was short. It also showed that catalyst could be reused for many times and the isolated yield of adipic acid was still stable.SO₄^2-/ZrO₂ solid acid catalyst was prepared by hydrothermal method. The catalysts were characterized with XRD and IR. The liquid phase esterification of acetic acid and 1-butanol was performed to confirm the optimal conditions. At the same time, the influence of different factors on conversion of acetic acid was studied. The test results showed in esterification reaction the technological conditions of n-butyl acetate were as follows: the reaction time was 2h, n （n-butanol）: n （acetic acid）=2:1, and w（catalyst） was 0.2% based on the total mass of initial materials. Conversion of acetic acid amounted to 99.1%. However, the conversion of acetic acid would decrease when the amount of WO₃ increased. Because the addition of WO₃ led to the reduction of the catalyst’s B. E. T surface area.更多还原