Ru-MACHO催化甘油加氢还原二氧化碳  

Carbon Dioxide Hydrogenation With Glycerol Over Ru-MACHO Catalysts

作　　者：沈峥[1,2] 王晨璐 刘诗扬 张唯[1,2] 黄欣[1,2] 张亚雷[1,2] SHEN Zheng;WANG Chenlu;LIU Shiyang;ZHANG Wei;HUANG Xin;ZHANG Yalei(State Key Laboratory of Pollution Control and Resource Reuse,Tongji University,Shanghai 200092,China;National Engineering Research Center of Protected Agriculture,Tongji University,Shanghai 200092,China)

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：《石油学报（石油加工）》2018年第5期897-903,共7页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金(21376180;21676205)资助

摘　　要：为解决传统二氧化碳加氢反应中需要大量氢气作为还原剂的问题,选用甘油作为还原剂,不仅降低生物柴油生产成本,也使还原过程更加安全、绿色、可持续。选用含钌螯合物Ru-MACHO为催化剂,进行催化甘油还原二氧化碳的研究,实现二氧化碳转化为甲酸的同时可将甘油转化为乳酸。考察了碳酸氢钾投加量、氢氧化钾投加量、反应温度、反应时间对反应的影响,并进行了工业级甘油试验、催化剂回用及反应路径推测的研究。结果表明,80mmol甘油和2.00g KHCO3可在1.12g KOH和3 mg Ru-MACHO催化条件下,经200℃,24h生成4.14mmol甲酸和21.04mmol乳酸,甘油和碳酸氢钾转化率分别达26.30%和20.70%。回用研究表明,此体系经5次回用后仍具有较高活性。从这些结果可以看出,Ru-MACHO对催化甘油还原二氧化碳有显著效果,为实现生物质资源化提供基础数据。In order to overcome the problem that large amount of H 2 is required for the process of traditional carbon dioxide(CO 2)hydrogenation,glycerol is used as the reductant,leading to a safe,green and sustainable reduction process and reducing the cost of biodiesel production as well.An efficient catalytic process combining the dehydrogenation of glycerol to lactic acid and the hydrogenation of CO 2 to formic acid over Ru-MACHO catalysts was developed.The effects of KHCO 3 dosage,KOH dosage,reaction temperature and reaction time on the yields of formic acid and lactic acid were discussed.Furthermore,the reaction behavior of industrial glycerol,recycling of catalyst,and plausible pathway was investigated.Under the conditions of 1.12 g KOH,3.0 mg Ru-MACHO catalyst,reaction temperature of 200℃,reaction time of 24 h,2.00 g KHCO 3,glycerol of 80 mmol,the amount of formic acid and lactic acid obtained were 4.14 mmol and 21.04 mmol.The conversion of glycerol and KHCO 3 are 26.30%and 20.70%,respectively.The catalysts can be recycled,exhibiting constant activity within 5 times.The results show that Ru-MACHO catalysts promote the reaction of CO 2 hydrogenation with glycerol,providing fundamental information on the utilization of biomass resources.

关 键 词：甘油 二氧化碳 加氢 Ru-MACHO催化剂 甲酸 乳酸 

分 类 号：O643[理学—物理化学]