Study on reaction for chemical refinery using biomass as resources

为了转化利用生物质作为化工原料，对糖型生物质的化学反应进行了研究。本研究主要包括两个部分：1）糖型生物质在高温高压水中的降解反应研究; 2）降解中间产物催化转化为芳烃和烯烃的研究。在关于生物质降解的研究的第一部分中，使用葡萄糖作为模型原料，并在200至300摄氏度的近临界条件下在水中反应，并添加各种催化剂。在没有催化剂的情况下，葡萄糖异构化为果糖，并主要转化为5-羟甲基糠醛（5-HMF）。在碱性催化剂的作用下，还原脱水生成5-HMF，并通过逆羟醛缩合反应得到乙二醇醛和二羟基丙酮等产物。当加入酸催化剂时，脱水的中间体5-HMF以高产率转化为有机酸，特别是乙酰丙酸。还发现葡萄糖向乙酰丙酸的转化在高于30重量%的高葡萄糖浓度下进行。在第二部分的研究中，有机酸如乙酰丙酸和乙酸的转化在沸石催化剂的存在下进行。从该研究中发现，有机酸被有效地转化为酮，并最终转化为芳香族化合物和低碳数烯烃的混合物。该反应可以在水的存在下进行。还发现，最终产物可以通过重力相分离非常容易地与水分离，这意味着不需要蒸馏。通过本研究，获得了有关催化剂性能和催化反应器的许多信息。

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.