Recovery of chemicals from sugar in supercritical fluids for oligochemistry cycle

从超临界流体中的糖中回收化学物质用于寡化学循环

• 批准号: 13555211
• 负责人: ADSCHIRI Tadafumi
• 金额: $ 4.61万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13555211/
• 关键词: Supercritical fluids; water; cellulose; Sugar; hydrolysis; reaction mechanism; 超臨界水; 反応速度; 有機合成; レトロアルドール縮合; 脱水反応; 異性化反応; アミド化; 糖類

We investigated chemical recycling from sugar in supercritical water, focusing on glycol acid as a biodegradable material. In this research, process conditions are surveyed to recover glycol aldehyde.First of all, we analyzed decomposition process of glycol using micro-reactors. Glycols decomposed to erythrose and then glycol aldehyde by retroaldol reaction. Glycol aldehyde is converted info fructose by tautomerism and finally decomposed into glyceraldehyde and pyruvaldehyde. These reactions were accompanied with dehydration.We estimated the reaction rate and its dependency on temperature and revealed that higher temperature and lower water concentration promotes retroaldol reaction instead of dehydration and tautomerism. The reaction at 450℃ in water with a density of 0.1 g/cm3 produced glycol acid with a yield of 89%. We also confirmed glycol aldehyde reacted into glycol acid by Cannizzaro reaction.The reaction rate was estimated as several tens msec, indicating that small reactor is required to enable industrial processes. We showed that the remained research theme are reaction conditions for conversion to glycol acid, reaction of concentrated reactants for industrial process, and utilization of heat from other industry.

我们研究了超临界水中糖的化学回收，重点是乙二醇酸作为一种可生物降解的材料。本研究考察了回收乙二醇醛的工艺条件。首先，分析了微反装置中乙二醇的分解过程。乙二醇通过逆羟醛反应分解为赤藓糖，然后分解为乙二醇醛。乙二醇醛通过互变异构转化为果糖，最后分解为甘油醛和异戊醛。这些反应都伴随着脱水，我们估计了反应速率及其对温度的依赖性，发现较高的温度和较低的水浓度促进了逆羟醛反应，而不是脱水和互变异构。在450℃下，在密度为0.1g/cm ~ 3的水中反应生成乙二醇酸，产率为89%。我们还证实了乙二醇醛通过Cannizzaro反应生成乙二醇酸，反应速率估计为几十毫秒，这表明需要小型反应器才能实现工业化过程。研究表明，乙二醇酸的转化反应条件、工业浓缩反应物的反应和其他工业热量的利用是今后的研究方向。

项目成果

M.Sasaki et al.: "Production of cellulose II from native cellulose by near-and supercritical water solubility"Journal of Agricultural and Food Chemistry. 51. 5376-5381 (2003)

M.Sasaki 等人：“通过近临界和超临界水溶性从天然纤维素生产纤维素 II”农业和食品化学杂志。

M.Sasaki et al.: "Conversion of lignin with supercritical water-phenol mixtures"Energy & Fuels. 17. 922-928 (2003)

M.Sasaki 等人：“用超临界水-苯酚混合物转化木质素”能源

K.Sue, et al.: "Apparatus for direct pH measurement of supercritical aqueous solutions"Journal of Supercritical Fluids. 28. 287-296 (2004)

K.Sue 等人：“超临界水溶液直接 pH 测量装置”超临界流体杂志。

Sue, K ら: "Apparatus for direct pH measurement of supercritical aqueous solutions"Journal of Supercritical Fluids. 28. 287-296 (2004)

Sue，K 等人：“超临界水溶液直接 pH 测量装置”，超临界流体杂志 28. 287-296 (2004)。

Takafumi Sato, Gaku Sekiguchi, Motofumi Saisu, Masaru Watanabe, Tadafumi Adschiri, Kunio Arai: "Dealkylation and Rearrangement Kinetics of 2-Isopropylphenol in Supercritical Water"Ind. Eng. Chem. Res.. 41(3). 3124-3130 (2002)

Takafumi Sato、Gaku Sekiguchi、Motofumi Saisu、Masaru Watanabe、Tadafumi Adschiri、Kunio Arai：“超临界水中 2-异丙基苯酚的脱烷基化和重排动力学”Ind。