微藻种类对其热解质量损失规律和产物及动力学的影响  

Weight-loss characteristics, components of bio-oil and kinetics during pyrolysis from different types of microalgae

作　　者：王浚浩 张雨 杨优优 左照江[3] 马中青[1] Wang Junhao;Zhang Yu;Yang Youyou;Zuo Zhaojiang;Ma Zhongqing(School of Engineering,Zhejiang Provincial Collaborative Innovation Center for Bamboo Resources and High-Efficiency Utilization,Zhejiang A&F University,Lin’an 311300,China;School of Agriculture and Food Science,Zhejiang A&F University,Lin’an 311300,China;School of Forestry and Bio-technology,Zhejiang A&F University,Lin’an 311300,China)

机构地区：[1]浙江农林大学工程学院浙江省竹资源与高效利用协同创新中心,临安311300 [2]浙江农林大学农业与食品科学学院,临安311300 [3]浙江农林大学林业与生物技术学院,临安311300

出　　处：《农业工程学报》2018年第19期239-247,共9页Transactions of the Chinese Society of Agricultural Engineering

基　　金：国家自然科学基金(51706207);中国博士后科学基金(2017M611987);浙江省自然科学基金(LQ17E060002);浙江省与中国林科院省院合作林业科技项目(2017SY01);浙江省竹资源与高效利用协同创新中心开放基金(2017ZZY2-02)

摘　　要：微藻是一种新型的可再生生物质资源,采用快速热解技术,可得到高品质的先进液体燃料和高附加值化学品。该文采用热重-红外联用仪、快速热解-气质联用仪和分布式活化能动力学模型(distribution activation energy model,DAEM)对莱茵衣藻(Chlamydomonas reinhardtii,CDR)、小球藻(Chlorella vulgaris,CRV)和铜绿微囊藻(Microcystis aeruginosa,MCA)的热解行为开展了研究,系统地对比了3种微藻在化学组成、热解失重规律、动力学、热解产物等方面的差异,并对微藻的热解机理进行了探讨。结果表明:1)3种微藻的热解过程可分为3个阶段,分别为干燥段、快速热解段和炭化阶段,其中铜绿微囊藻失重率最大,达到17.34%/min,且随着升温速率的增加,TG/DTG(thermogravimetry/differential thermogravimetry)曲线往高温一侧移动;2)红外光谱分析结果表明微藻热解主要产物为CH4、CO2、含C=O键的脂肪酸、含N-H键和C-N键的酰胺类化合物,其中莱茵衣藻热解产生的CH4质量分数最高,铜绿微囊藻热解产生的含C=O键化合物质量分数最高;3)铜绿微囊藻的活化能数值最高,随着转化率增加,活化能从100增加到680 k J/mol;4)Py-GC/MS分析表明小球藻热解产生的含氧化合物质量分数最高,达到30.89%,铜绿微囊藻热解产生的酚类化合物、芳香族碳氢化合物、胺和酰胺类和其他含氮化合物的质量分数最高,分别达到10.41%,13.46%,13.87%和14.27%。本文可为微藻的能源化利用提供科学和基础数据。As a kind of new-fashionable biomass material,microalgae has the advantages of large amount,fast-growing,high efficiency of photosynthesis,and less land for cultivating.Biomass fast pyrolysis technology is a promising technology to convert low-grade microalgae into high value-added advanced liquid bio-fuels and bio-chemicals.In this paper,a systematical comparison of components’content,pyrolysis behaviors,kinetics,and evolved gas components,was carried out among 3 types of microalgae(Chlamydomonas reinhardtii,Chlorella vulgaris,and Microcystis aeruginosa)using thermogravimetric analyzer coupled with Fourier transform infrared spectrometry(TGA–FTIR),pyrolyzer coupled with gas chromatography/mass spectrometer(Py–GC/MS),and distributed activation energy model(DAEM).The result showed that:(1)Based on the TGA analysis,the thermal degradation process of microalgae was composed of 3 stages,namely drying stage(temperature range of 30-150℃),fast pyrolysis stage(temperature range of 150-550℃),and carbonization stage(temperature range of 550-800℃),and the maximum weight loss rate was observed for Microcystis aeruginosa with a value of 17.34 wt.%/min;the TG/DTG(thermogravimetry/differential thermogravimetry)curves moved to the side of high temperature and the weightlessness rate unit time(wt.%/min)gradually increased as the heating rate increased.(2)The FTIR analysis indicated that there were 6 strong infrared characteristic absorption bands from microalgae pyrolysis,which located at 3734 cm– 1(-OH),2 938 cm-1(-CH3),2 360 cm-1(-C=O),1 770 cm-1(C=O),950 cm-1(P-O-P)and 667 cm-1(CO2).These characteristic functional groups represented the main evolved gas components were CH4,CO2,compounds containing C=O bond,compounds containing N-H and C-N bonds,in which the maximum content of CH4 was evolved from Chlamydomonas reinhardtii,and the maximum content of compounds containing C=O bond was evolved from Microcystis aeruginosa.(3)Based on DAEM analysis,as conversion rate increased,the activation energy values of 3 types of

关 键 词：热解 动力学 微生物 微藻 热重-红外联用 热解-气质联用 

分 类 号：S216[农业科学—农业机械化工程]