固体磺酸催化H2O2氧化醛生成羧酸的研究-工业催化专业论文.docxVIP

摘要中文摘要 摘要 中文摘要 醛类化合物催化氧化合成羧酸这类反应无论在有机合成还是在精细化工中 都有重要的意义和应用价值。本论文研究了固体磺酸催化过氧化氢氧化醛类化 合物生成羧酸的反应体系。该体系在温和的条件下，可以实现醛到羧酸的转化， 并且催化剂可以循环使用。 论文首先考察以磺酸树脂Amberlystl5催化过氧化氢氧化苯甲醛，结果发现 在90℃，反应7 h，催化剂的量为5 wt％，H202的量为30 mmol(1．5 equiv)时， 不使用溶剂，苯甲醛的转化率达到85％，使用乙酸作溶剂时，苯甲酸的分离收 率达到95％。应用此催化体系催化其它醛的氧化同样表现出较好的催化活性， 有缺电子取代的芳香醛和脂肪醛几乎定量生成相应的羧酸。而且Amberlystl5是 可以回收循环使用的催化剂，使用三次后，催化活性只略微降低，但是此催化 剂机械强度不高，易破碎成细小颗粒。 制备了更稳定的磺化碳材料，考察了碳前体和磺化温度的影响，结果发现 以淀粉为原料，在150℃磺化时制备的磺化碳材料催化苯甲醛氧化活性最高， 而且引入磺酸基的量最大，为1．0 mmol／g。此催化剂在重复使用一次后，活性略 微降低，之后重复使用两次，活性基本不变，表明制备的磺化碳材料是可以循 环使用的催化剂。该催化剂也可用于其它醛类化合物的催化氧化，但是相同条 件下，催化活性比磺酸树脂略低，可能由于磺酸树脂磺酸基的量大于制备的磺 化碳材料。 关键词：醛；羧酸；固体磺酸；过氧化氢；氧化 AbstractAbstract Abstract Abstract The transformation of aldehydes to carboxylic acids is all important reaction in organic synthesis and fine chemical industry．This thesis studied the oxidation of aldehydes to carboxylic acids using H202 as oxidant catalyzed by solid sulfonic acid． This catalytic oxidation system could efficiently transform aldehydes to carboxylic under mild conditions，and the catalyst is recyclable． Firstly the oxidation of benzaldehyde to the benzoic acid catalyzed by sulfonic acid resin Amberlyst 1 5 using 30％H202 as the oxidant was investigated．nle conversion of benzaldehyde reached 85％under 90 oC for 7 h using 5 wt％Amberlyst 1 5 and 1．5 equiv HE02．And the yield of benzoic acid was improved to 95％when acetic acid was used as the solvent．The catalytic system also showed good catalytic activity in the oxidation of other aldehydes．Benzaldehyde derivatives、析m electron-withdrawing group and aliphatic aldehydes were almost quantitatively convened into their corresponding acids．Amberlyst 1 5 was all efficient，recyclable heterogeneous catalyst for the oxidation of benzaldehyde to benzoic acid by H202, which can be recycled for two times and the activity of the catalyst only decreased a little in the third run．But the mechanical strength of Amberlyst 1 5 was not hJ}gh and easy to break into small particles． The more stable solid catal