金属-离子液体催化剂及直接合成己内酰胺反应过程的研究-化学工艺专业论文.docxVIP

河北工业大学硕士学位论文 河北工业大学硕士学位论文 金属- 金属-离子液体催化剂及直接合成己内酰胺反应过程的研究 金属-离子液体催化剂及直接合成己内酰胺反应过程的研究 摘 要 本文以环己酮、硝酸根离子和氢气为原料，通过改变催化剂、调控反应条件，一锅法 合成了环己酮肟和己内酰胺。 结果表明，以 Pd 为加氢催化剂时，硝酸根离子加氢合成羟胺的反应较适宜的反应条 件为：反应压力 1.9MPa，催化剂用量与原料 NaNO3 加入量的比为 1：99，反应温度 95℃。 以 Pd 和 Pt 为加氢催化剂时，环己酮、硝酸根离子和氢气一锅法合成环己酮肟的反应 较适宜的反应条件为：反应温度 75℃，反应时间 8h，反应压力 1.3Mpa，此时环己酮肟收 率最高为 7.6%。SBA-15 作为催化剂的载体效果较好。Pd 负载量为 4%，Pt 负载量为 1% 时催化剂催化效果较好。反应较佳的 pH 为 1.41，反应液中甲苯的加入量与原料环己酮加 入量的体积比为 0.6 时环己酮肟的收率最高。 另外，我们采用了[HSO3-b-N(CH3)3]HSO4 和有机胍盐[TMG][TsO]两种离子液体研究金 属-离子液体催化剂对环己酮、硝酸根离子和氢气一锅法合成环己酮肟和己内酰胺的催化效 果。Pd8%-[HSO3-b-N(CH3)3]HSO4 对环己酮、硝酸根离子和氢气一锅法合成环己酮肟的催 化效果最好，环己酮肟的收率达到 1.9%。环己酮、硝酸根离子和氢气一锅法合成己内酰胺 的路线是可行的，目前己内酰胺收率最高达到 0.7%。 关键词：一锅法合成，环己酮肟，己内酰胺，离子液体 i PAGE PAGE iv STUDY ON METAL-IONIC LIQUID CATALYST AND REACTION OF DIRECT SYNTHESIS OF ε-CAPROLACTAM ABSTRACT One-pot synthesis of cyclohexanone oxime and caprolactam by the reaction of cyclohexanone with nitrate ion and hydrogen was investigated in the present work. The results showed that the optimized reaction conditions of the synthesis of hydroxylamine by the reaction of nitrate ion with hydrogen catalyzed by Pd were nitrate ion and hydrogen conducted at 95℃ and 1.9Mpa catalyzed by Pd/SiO2 catalyst the ratio of whose quality and the quality of raw material NaNO3 was 1:99。 The optimized reaction conditions of the synthesis of cyclohexanone oxime by the reaction of cyclohexanone with nitrate ion and hydrogen catalyzed by Pd and Pt were cyclohexanone and nitrate ion and hydrogen conducted at 75℃ and 1.3Mpa for 8h，and more than 7.6% yield of cyclohexanone oxime was obtained under the optimized reaction conditions.The better catalyst support was SBA-15 and the best catalyst was Pd4%+Pt1%/SBA-15. A higher yield of cyclohexanone oxime was obtained by means of adding some toluene the ratio of whose volume and the volume of cyclohexanone was 0.6 to the reaction solution and adjusting pH to 1.41. In addition，one-pot synthesis of cyclohexanone oxime and caprolactam by the rea