碳水化合物在乙醇介质中催化转化规律的分析-analysis of the catalytic conversion law of carbohydrate in ethanol medium.docxVIP

万方数据 万方数据 摘要 果糖为原料时，探究了反应温度、反应时间、硫酸浓度和乙醇/正己烷的不 同比例对果糖反应产物分布规律的影响。反应温度较低或者反应时间较短时， 果糖醇解的主要产物是乙氧基甲基糠醛。果糖浓度为 20g·L-1 ，反应温度为 120 ℃，反应时间为 180 min，硫酸浓度为 0.1 wt%，乙醇/正己烷体积比为 6:4 时，收率达到 66.29%。同时正己烷在高温下比在低温下对产物分布的影响更为 显著。 构建乙醇/正己烷/水三元反应溶剂体系中，考察了葡萄糖、果糖在此体系中 生成产物的分布规律。在两相反应体系中，产物主要集中在反应液的下层，在 上层溶液中含量较少。葡萄糖作为原料时，反应体系中固定乙醇的体积分数， 随着水含量的增加，乙酰丙酸乙酯和 5-乙氧基甲基糠醛的收率呈下降趋势；反 应体系中固定了水的含量，乙酰丙酸的收率基本保持不变，随着乙醇含量的减 少，乙酰丙酸乙酯和 5-乙氧基甲基糠醛的收率呈下降趋势。果糖为原料时，在 反应温度为 120 ℃时，产物分布变化趋势与葡萄糖基本一致。当反应温度为 180 ℃时，在反应体系中水的体积分数为 10%时，随着正己烷含量的增加，或 者当反应体系中固定了乙醇的体积分数为 50%时，随着水含量的增加，5-乙氧基 甲基糠醛的收率均出现了先增加后下降的趋势。反应体系中水含量越多，有利 于乙酰丙酸的生成，而不利用 5-乙氧基甲基糠醛和乙酰丙酸乙酯的生成；反应 体系中乙醇的含量对乙酰丙酸乙酯的收率影响较显著。 关键词：超低酸 碳水化合物 乙酰丙酸乙酯 5-乙氧基甲基糠醛 反应溶 剂体系 II Abs Abstract Abstract Biomass is renewable resources on the earth that can replace the petroleum-based chemicals. Carbohydrates, are the most plentiful element in biomass resources, can be converted into a variety of high valuable chemicals by biological or chemical pathways. Recently the research on ethyl levulinate and 5-ethoxymethyfurfural from biomass becomes hot. In this research, the distribution of products from glucose and fructose ethanolysis catalyzed by extremely low sulfuric acid in ethanol, ethanol/n-hexane, ethanol/n-hexane/water medium was investigated in low boiling point organic solvent. A series studies aiming at three types of solvent systems for biomass conversion were performed, including the distribution of products from biomass in different processing conditions, the reaction pathway of biomass alcoholysis. Specifically, conversion of glucose and fructose in different reaction systems was selected as the representative route for detailed study. Extremely low sulfuric acid (≤0.1wt%) was used as catalyst. The distribution of products from glucose and fructose ethanolysis was studied. The experiment results indicated the fructose can be converted easily and the yield of ethyl levulinate was much higher compared with the result obtained from glucose with lower reaction temperatu