Study on reaction for chemical refinery using biomass as resources

为了将生物质转化为化工原料并加以利用，对糖类生物质的化学反应进行了研究。本研究由两部分组成：1)糖型生物质在高温高压水中的降解反应研究；2)降解中间体催化转化为芳烃和烯烃的研究。在生物质降解研究的第一部分，以葡萄糖为模型原料，在200-300摄氏度的近临界条件下，添加各种催化剂，在水中进行反应。在没有催化剂的情况下，葡萄糖异构化为果糖，主要转化为5-羟甲基呋喃甲醛(5-HMF)。在碱性催化剂的作用下，5-羟甲基呋喃的脱水反应被还原为乙二醇醛和二羟基丙酮。加入酸性催化剂后，脱水中间体5-HMF高产率地转化为有机酸，特别是乙酰丙酸。研究还发现，当葡萄糖浓度超过30wt%时，葡萄糖转化为乙酰丙酸的反应是进行的。第二部分研究了在沸石催化剂存在下，乙酰丙酸和醋酸等有机酸的转化反应。研究发现，有机酸可以有效地转化为酮，最终转化为低碳数的芳香族化合物和烯烃的混合物。这个反应可以在有水的情况下进行。通过重力相分离，最终产物可以很容易地从水中分离出来，这意味着不需要蒸馏。通过这项研究，获得了许多关于催化剂性能和催化反应器的信息。

In order to convert and utilize biomass as raw material of chemical industry, chemical reaction of sugar type biomass was investigated. The study consists of two parts: 1) the research on degradation reaction of sugar type biomass in water of high temperature and high pressure, 2) the research on the catalytic conversion of the degradation intermediate into aromatic and olefin hydrocarbons. In the first part of the study concerning the degradation of biomass, glucose was used as a model raw material and reacted in the water under a near critical condition at 200 to 300 degree Celsius with addition of various catalysts. Without catalyst, glucose was isomerized to fructose and mainly converted to 5-hydroxylmethyl-furfural (5-HMF). With addition of basic catalyst, dehydration to 5-HMF was reduced, and the products such as glycol aldehyde and dihydroxyacetone were obtained by retro-aldol reaction. When acid catalyst was added, the dehydrated intermediate 5-HMF was converted to organic acid, especially, levulinic acid at a high yield. It was also found that the conversion of glucose to levulinic acid proceeded at a high glucose concentration more than 30 wt%. In the second part of the study, the conversion of organic acids such as levulinic acid and acetic acid was performed in the presence of zeolite catalyst. It was found from this research that the organic acids were efficiently converted to ketones and finally to the mixture of aromatic compounds and olefin hydrocarbons of lower carbon numbers. This reaction could proceed in the presence of water. It was also found that the final products could be separated from water very easily by gravitational phase separation, which means that distillation is not necessary. From this study, many information about catalyst performance and catalytic reactor were obtained.