催化酯化升级生物质油  

Upgrading of Bio-oil by Catalytic Esterification

作　　者：程岩岩 隋光辉 陈志敏 魏庆玲 段亚军 王晓峰[1] 杨晓敏[1] 王子忱[1] CHENG Yanyan;SUI Guanghui;CHEN Zhimin;WEI Qingling;DUAN Yajun;WANG Xiaofeng;YANG Xiaomin;WANG Zichen(College of Chemistry,Jilin University,Changchun 130012,China)

机构地区：[1]吉林大学化学学院,长春130012

出　　处：《高等学校化学学报》2018年第12期2746-2751,共6页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:51502108);吉林省发改委自主创新能力专项(批准号:2014N145)资助

摘　　要：以稻壳热解油为原料,采用减压蒸馏法将生物质油轻组分和重组分分离.由生物质油重组分通过催化酯化反应制备了乙醇生物质油,对催化剂硫酸采用纳米碳酸钙沉淀法进行分离,从而实现生物质油的品质升级.以生物质油的pH值作为评价升级反应的指标,考察了催化酯化反应条件和后处理条件的影响.采用气相色谱-质谱联用(GC/MS)和凝胶色谱(GPC)研究了稻壳热解油和乙醇生物质油的组成和分子量的变化.实验结果表明,在催化酯化过程中,当反应温度为120℃,反应时间为3 h,硫酸用量为4 g,溶剂为无水乙醇时,乙醇生物质油的pH值可达5. 86.在催化剂中和过程中,中和剂对乙醇生物质油pH值的影响顺序为BaO≈BaCO_3<CaCO_3<nano-CaCO_3<CaO.经过催化酯化升级过程,不仅乙醇生物质油中的酯类物质增加了26. 1%,酸类物质和酚类物质分别减少了15. 9%和12. 8%,而且乙醇生物质油的分子量也降低了90%.Bio-oil pyrolyzed from rice husk was separated into light-oil and heavy-oil by vacuum distillation.The heavy-oil was upgraded by catalytic esterification with sulfuric acid to prepare ethanol-bio-oil.Then the sulfuric acid catalyst was separated from ethanol-bio-oil using neutralizer.Effects of the catalytic esterification and neutralization on the pH value of ethanol-bio-oil were investigated.The component and molecular weight of raw bio-oil and the ethanol-bio-oil were analyzed by GC/MS and GPC.The results show that the pH value of ethanol-bio-oil can reach 5.86 under the following optimized reaction conditions,120℃,3 h,sulfuric acid as catalyst,ethanol as solvent.The influence sequence of neutralizers on the pH value of ethanol-bio-oil is as following,BaO≈BaCO3<CaCO3<nano-CaCO3<CaO.In addition,after the progress of catalytic esterification,not only did esters increase by 26.1%,acids and phenols in ethanol bio-oil decrease by 15.9%and 12.8%,respectively,but also did the molecular weight of ethanol-bio-oil decrease by 90%.

关 键 词：生物质油升级 乙醇生物质油 中和剂 催化酯化 

分 类 号：O643[理学—物理化学] O69[理学—化学]