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Solid-phase Hydrogenation of Organic Compounds over Metal Catalysts

金属催化剂上有机化合物的固相加氢

基本信息

批准号：
03804038
负责人：
HARADA Tadao
金额：
$ 1.22万
依托单位：
Ryukoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1991
资助国家：
日本
起止时间：
1991 至 1992
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03804038/
关键词：
Solid phase reaction Hydrogenation Product analysis Catalyst inhibitor Fine nickel powder Disodium fumarate Disodium maleate 水素化反応異性化反応

项目摘要

Study on the solid-phase hydrogenation over a metal catalyst was carried out, using disodium fumarate and maleate as substrates and fine nickel powder as a catalyst. In the course of this study, it was found that the substrates were hydrogenated to disodium succinate even in the process of product analysis in the liquid phase. Thus, the development of a product analysis procedure to estimate the amount of disodium succinate formed in the solid phase was strongly required. An inhibitor treatment of the nickel catalyst was found to satisfy the requirement. A typical experimental procedure is as follows ; after the solid phase reaction, a methanol solution of catalyst inhibitor(e. g., sodium iodide and cysteine methyl ester hydrochloride) is added to the reaction mixture(Ni+substrate+product(s)). The inhibitor treatment of the nickel catalyst is followed by the extraction of the substrate and product(s) with H_2O *the esterification of the substrate and product(s)*GLC analysis. By the application of this procedure it was made clear that the amount of succinate formed in the solid phase was only 0.04mmol/g Ni in the maximum at 30ﾟC and at 1x10^5Pa hydrogen pressure, although a large excess of hydrogen gas was present in the reaction system. This finding suggests that a small amount of the substrate would be hydrogenated with dissociated hydrogen on the nickel surface and the hydrogen gas in the reaction system could not be consumed for the solid phase reaction under the above reaction conditions. The studies on the solid phase hydrogenation under severer conditions (higher temperature, higher pressure) are now in progress.

以富马酸二钠和马来酸二钠为底物，超细镍粉为催化剂，进行了金属催化剂上的固相加氢反应研究。在本研究过程中，发现底物加氢生成琥珀酸二钠，即使在产品分析的过程中也是如此。因此，开发一种产品分析程序来估计在固相中形成的琥珀酸二钠的量是非常必要的。镍催化剂的缓蚀剂处理达到了要求。典型的实验步骤如下：固相反应后，将含有催化剂缓蚀剂(如碘化钠和半胱氨酸甲酯盐酸盐)的甲醇溶液加入反应混合物(Ni+底物+产物(S))。镍催化剂的缓蚀剂处理后，用水萃取底物和产物(S)，底物和产物的酯化(S)*GLC分析。结果表明，尽管反应体系中存在大量过剩的氢气，但在30ﾟC和1×10~(-5)PaH_2压力下，固相中生成的琥珀酸量最大，仅为0.04 mm o l/g Ni。这一发现表明，在上述反应条件下，少量底物会与镍表面的离解氢发生氢化反应，反应体系中的氢气不能用于固相反应。在更恶劣的条件下(更高的温度、更高的压力)进行固相加氢的研究正在进行中。