DESIGN OF CATALYST FOR UTILIZATION OF CO2 WITH HIGH PRESSURE-HIGH TEMPERATURE IN SITU INFRARED METHOD

1)装置设计了一种可在1 MPa、600 K下工作的不锈钢高压高温红外池，用于高压连续流反应系统中作为反应器。利用该原位红外池进行了二氧化碳和氢气合成甲醇的实验。对所得数据的分析表明，该反应的反应中间体应该是铜上的甲酸盐物种。这与我们以前提出的反应机理是一致的。2）甲醇合成催化剂的设计作为该方法的应用之一，对CO_2和H_2合成甲醇的催化剂设计进行了研究。为了控制甲酸盐与铜的反应活性，研究了载体的影响。工作假设如下：中间体的数目应随着铜上的电子密度的增加而增加，然后降低电子密度使甲酸盐物种对氢化反应敏感。TiO 2的增强效果最好，并讨论了甲酸盐对TiO 2的作用。3）CO_2加氢产物分布的控制研究结果表明，控制甲酸盐对铜的影响是非常重要的。然后对二氧化碳加氢反应产物的控制进行了如下尝试：（1）设计助催化剂如酸碱组分，控制甲醇合成反应。(2)通过添加用于C-C键形成或用于氢化的金属来设计双功能活性。其可产生烃和氧化烃。(67th日本Catal.Soc.的会议）。

1) ApparatusA stainless steal high pressure-high temperature infrared cell was designed to be used under lMPa, 600K.It was used as a reactor in the high pressure coutinuous flow reaction system. Mthanol synthesis from carbon dioxide and hydrogen was conducted using this in situ infrared cell. The analysis of obtained data suggested that the reaction intermediates of this reaction should be the formate species on copper. This agreed with our previous proposal on the reaction mechanism. The design and operation of the in situ IR cell were summarized in "Kagakukougaku".2) Design of methanol synthesis catalystAs one the applications of this method, design of the catalyst for methanol synthsis from CO2 and H2 was studied. In order to control the reactivity of formate on copper, effect of support was investigated. The working hypothesis was as follows ; the number of intermediates should be enhanced with increasing the electron density on copper then decreasing the electron density made the formate species sensitive for hydrogenation reaction. TiO2 showed the highest enhancement effect, and the role of formate on titania was discussed. These results were published on Res.Chem.Intermed.3) Control of product distribution of CO2 hydrogenationThe results showed the importance of control of formate on copper. Then the control of reaction products of hydrogenation of carbon dioxide was tried as follows :(1) Desing of co-catalyst such as acid-base components, to control the methanol synthesis reaction.(2) Design of bi-functional activity by adding metals for C-C bond formation or for hydrogenation. which could porduce hydrocarons and oxygenated hydrocarbons. (67th meeting of Catal.Soc.of Japan).