甘油水热碱催化还原H_2O和CO_2的过程  

Solvent Isotope Effect on Reduction of H_2O or CO_2 with Glycerine Under Alkaline Hydrothermal Condition

作　　者：沈峥[1,2] 顾敏燕[1] 周雪飞[1] 张亚雷[1] 

机构地区：[1]同济大学污染控制与资源化研究国家重点实验室,上海200092 [2]同济大学国家设施农业工程技术研究中心,上海200092

出　　处：《同济大学学报（自然科学版）》2015年第5期722-728,共7页Journal of Tongji University:Natural Science

基　　金：国家自然科学基金(21376180);国家"八六三"高技术研究发展计划(2013AA103006);中央高校基本科研业务费专项资金(2870219021);青浦区-同济大学科技合作项目(20143289)

摘　　要：结合氢谱核磁共振(1 H-NMR)、氘谱核磁共振(2 HNMR)、高效液相色谱-质谱(LC-MS)和气相色谱-质谱(GCMS)分析方法,调查了水热碱催化条件下甘油还原水和二氧化碳过程中通过重水(D2O)代替H2O的溶剂同位素效应.研究表明:乳酸分子上β-碳的氢完全被替换成氘(D),说明甘油分子上2-碳位的羟基首先转化为羰基,接着再转为乳酸分子上的羟基;产生的氢气和甲酸中存在大量的D,说明水分子作为反应产物参加了反应;产生的氢气和甲酸中D%超过50%,说明甘油首先发生脱水反应而不是脱氢反应,最有可能的中间产物是丙酮醇.The solvent isotope effect was investigated with 1H-and 2H-NMR,LC-MS and GC-MS analyses on the reduction of H2O or CO2 with glycerine under alkaline hydrothermal conditions.The solvent isotope study results show that the H on the β-C of lactate is almost exchanged by D2O,which suggests that the hydroxyl （-OH） group on the 2-C of glycerine is first transformed into a carbonyl （C=O） group and then is converted back into a-OH group to form lactate;a large amount of D is found in the produced hydrogen gas or formic acid,which shows that the water molecules act as a reactant;and D％ in the produced hydrogen gas or formic acid is far more than 50％,which straight-forwardly shows that acetol is formed in the first place as the most probable intermediate by undergoing a dehydration reaction rather than a dehydrogenation reaction.

关 键 词：溶剂同位素效应 甘油 乳酸 水热反应 

分 类 号：X172[环境科学与工程—环境科学]