生物质热解油提质及其氧化动力学分析  

Upgrading of Biomass Pyrolysis Oil and Its Oxidation Kinetics

作　　者：梅德清[1] 王铖 任吴越 戴鹏飞[1] 郭冬梅 杜家益[1] MEI Deqing;WANG Cheng;REN Wuyue;DAI Pengfei;GUO Dongmei;DU Jiayi(School of Automobile and Traffic Engineering,Jiangsu University,Zhenjiang 212013,China)

机构地区：[1]江苏大学汽车与交通工程学院

出　　处：《石油学报（石油加工）》2019年第5期973-980,共8页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金项目(51761145011,51876082,51876133);江苏高校品牌专业建设工程资助项目(苏政发办[2014]82号);江苏省科技厅重点研发计划项目(BE2016139)资助

摘　　要：采用732型阳离子交换树脂为催化剂,通过预处理和催化酯化工艺对生物质热解油提质处理,获得精制生物油,分析比较生物质热解油提质前后的组分、低热值、黏度与pH值等燃料特性参数,并基于热重实验研究提质前后生物质热解油的氧化和燃烧特性。结果表明:对于100 mL粗制生物油,最佳的催化酯化反应条件为油/醇体积比2/1、催化剂用量8 g、反应温度50℃。GC-MS检测结果表明,经过酯化工艺,粗制生物油的酯类和酮类组分分别增加了82.4%和31.0%,而酸类、酚类、大分子醚类等组分分别下降了85.8%、18.0%、36.6%。与生物质热解油相比,精制生物油的pH值升高至5.7,低热值增加7.5%,黏度降低10.1%。在空气氧化氛围热重条件下,与生物质热解油相比,精制生物油的起始质量损失温度滞后6.1℃,但其在高温氧化阶段的平均氧化速率提高6.5%,因而终了质量损失温度提前5.3℃。依据生物质热解油提质前后的氧化反应动力学特性,将其热重条件下的挥发氧化质量损失分为失水蒸发、慢速分解、快速燃烧和碳化等4个一级反应过程,精制生物油在失水蒸发阶段比生物质热解油挥发所需的活化能略高,但在慢速分解、快速燃烧和碳化阶段比生物质热解油挥发所需的活化能低,综合整个氧化燃烧过程可见精制生物油更易氧化和燃烧。Refined bio-oil was obtained through pretreatment and catalytic esterification of biomass pyrolysis oil using 732 ion-exchange resin as catalyst.Then,characteristics of biomass pyrolysis oil and refined bio-oil,including composition,low calorific value,kinematic viscosity and pH value were analyzed and compared with each other.Oxidation and combustion characteristics of biomass pyrolysis oil and refined bio-oil were also investigated under thermogravimetric conditions.Experimental results indicate that,for 100 mL crude bio-oil,the optimum catalytic esterification conditions are oil and alcohol volume ratio of 2/1,8 g catalyst dosage and reaction temperature of 50℃.GC-MS results suggest that,after catalytic esterification,the fraction of esters and ketones in crude bio-oil increases 82.4%and 31.0%,respectively.However,the fraction of acids,phenols and macroethers in crude bio-oil decreases 85.8%,18.0%and 36.6%,correspondingly.Compared with crude bio-oil,pH value of refined bio-oil increases to 5.7,low calorific value increases 7.5%,and kinematic viscosity decreases 10.1%.Compared with the biomass pyrolysis oil,the results of thermogravimetric experiments under oxidative atmosphere show that,for refined bio-oil,its initial temperature of mass loss is enhanced 6.1℃,average oxidation rate is increased 6.5%at the stage of high temperature oxidation,and final temperature of mass loss is reduced 5.3℃.According to oxidation dynamic characteristics of biomass pyrolysis oil and refined bio-oil,the process of mass loss under thermogravimetric conditions can be divided into four stages:water evaporation,slow decomposition,rapid combustion and carbonization.It is found that the required activation energy for refined bio-oil volatilization at the stage of water evaporation is slightly higher than that of biomass pyrolysis oil.However,the required activation energy for refined bio-oil volatilization is less than that of biomass pyrolysis oil at other three stages,i.e.,stages of slow decomposition,rapid combustion and carb

关 键 词：生物质热解油 催化酯化 热重 氧化 热力学 

分 类 号：TK6[动力工程及工程热物理—生物能]