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王浚浩,张雨,杨优优,左照江,马中青.微藻种类对其热解质量损失规律和产物及动力学的影响[J].农业工程学报,2018,34(19):239-247.DOI:10.11975/j.issn.1002-6819.2018.19.031
微藻种类对其热解质量损失规律和产物及动力学的影响
投稿时间:2018-04-07  修订日期:2018-06-30
中文关键词:  热解  动力学  微生物  微藻  热重-红外联用  热解-气质联用
基金项目: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)
作者单位
王浚浩 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 
张雨 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 
杨优优 2. 浙江农林大学农业与食品科学学院临安 311300 
左照江 3. 浙江农林大学林业与生物技术学院临安 311300 
马中青 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 
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中文摘要: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 kJ/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。
Wang Junhao,Zhang Yu,Yang Youyou,Zuo Zhaojiang,Ma Zhongqing.Weight-loss characteristics, components of bio-oil and kinetics during pyrolysis from different types of microalgae[J].Transactions of the Chinese Society of Agricultural Engineering (Transactions of the CSAE),2018,34(19):239-247.DOI:10.11975/j.issn.1002-6819.2018.19.031
Weight-loss characteristics, components of bio-oil and kinetics during pyrolysis from different types of microalgae
Author NameAffiliation
Wang Junhao 1. School of Engineering, Zhejiang Provincial Collaborative Innovation Center for Bamboo Resources and High-Efficiency Utilization, Zhejiang A & F University, Lin'an, 311300, China
 
Zhang Yu 1. School of Engineering, Zhejiang Provincial Collaborative Innovation Center for Bamboo Resources and High-Efficiency Utilization, Zhejiang A & F University, Lin'an, 311300, China
 
Yang Youyou 2. School of Agriculture and Food Science, Zhejiang A & F University, Lin'an, 311300, China
 
Zuo Zhaojiang 3. School of Forestry and Bio-technology, Zhejiang A & F University, Lin'an, 311300, China 
Ma Zhongqing 1. School of Engineering, Zhejiang Provincial Collaborative Innovation Center for Bamboo Resources and High-Efficiency Utilization, Zhejiang A & F University, Lin'an, 311300, China
 
Key words:pyrolysis  kinetics  microorganisms  microalgae  TGA-FTIR  Py-GC/MS
Abstract: 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 microalgae increased. The activation energy of Microcystis aeruginosa increased from 100 to 680 kJ/mol, the activation energy of Chlorella vulgaris increased from 40 to 265 kJ/mol, and the activation energy of Chlamydomonas reinhardtii increased from 20 to 250 kJ/mol. Among the 3 types of microalgae, Microcystis aeruginosa had the maximum value of activation energy. (4) Based on the Py-GC/MS analysis, the whole components in the bio-oil could be divided into the following categories, such as alkanes, olefins, benzene series, alcohols, ethers, aldehydes, ketones, nitriles, furans, indoles, and acids. Among them, long-chain alkanes, olefins, aldehydes and ketones, fatty acids and esters were mainly derived from pyrolysis of lipids and carbohydrate, while phenols, aromatics, amines and amides, heterocyclic compounds containing nitrogen were mainly derived from pyrolysis of protein. Chlorella vulgaris produced the maximum content of oxygenates compounds reaching up to 30.89%, while Microcystis aeruginosa produced the maximum contents of phenols, aromatic hydrocarbons, amines and amides, and other compounds containing nitrogen reaching up to 10.41%, 13.46%, 13.87% and 14.27%, respectively. In summary, this paper would be useful to supply scientific and basic data for industrial application of microalgae.
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