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应用分布活化能模型分析伊敏褐煤丝炭腐植酸热解及氢气生成动力学
  • ISSN号:1000-6818
  • 期刊名称:Acta Physico - Chimica Sinica
  • 时间:2012.1.1
  • 页码:25-36
  • 分类:O643[理学—物理化学;理学—化学] O641[理学—物理化学;理学—化学]
  • 作者机构:[1]太原理工大学煤科学与技术教育部及山西省重点实验室,太原030024, [2]太原理工大学地球科学与工程系,太原030024
  • 相关基金:国家自然科学基金(41072116 40772097 40572094); 高等学校博士学科点专项科研基金(20091402110002)资助项目
  • 相关项目:低中煤级煤化作用非线性演化的地球化学机制及其动力学模型
中文摘要:

应用开放体系的热重-质谱(TG-MS)联用技术在5、20和50℃·min-1三个升温速率下对伊敏褐煤丝炭腐植酸(F-HA)和脱灰丝炭腐植酸(DF-HA)的热解行为进行了分析,并利用分布活化能模型(DAEM)分别对其热解和氢气生成动力学进行分析,获得了热解过程和氢气生成的活化能分布函数.结果表明:(1)F-HA热解活化能分布函数呈类Gaussian分布,且具有一定的对称性,主峰位与标准Gaussian分布相一致;DF-HA热解活化能分布函数也呈类Gaussian分布形式,主峰位与Gaussian分布相比,偏向低活化能值.根据转化率与温度、活化能的关系,结合腐植酸的热失重特征,将F-HA热解过程划分为四个阶段,DF-HA热解过程划分为五个阶段,并对腐植酸热解过程中各阶段的化学反应进行了详细讨论.(2)F-HA和DF-HA热解氢气生成活化能分布函数均呈类Gaussian分布,热解氢气生成活化能的整体趋势为随着转化率的升高而增加,但也表现出一定的阶段集中分布特征.根据热解氢气生成的动力学特征,将其生成过程划分为五个阶段,反映了其生成的不同化学反应机制.(3)酸洗脱灰对伊敏丝炭提取出的HA的热解行为、热解过程及热解氢气生成动力学产生了影响.

英文摘要:

The thermal behavior of humic acids of fusain (F-HA) and humic acids of demineralized fusain (DF-HA) were investigated at heating rates of 5,20,and 50℃·min-1 using an open system thermogravimetric analyzer coupled to a quadrupole thermogravimetry mass spectrometer (TG-MS).The pyrolytic and hydrogen generation kinetics were analyzed using the distributed activation energy model (DAEM) and the distribution functions of the activation energy were obtained.The results indicated:(1) the distribution function of the activation energy for F-HA has an asymptotic approximation to a Gaussian distribution during pyrolysis.Moreover,it has some symmetry properties and the same peak value as a standard Gaussian distribution.The distribution function of the activation energy for DF-HA has an asymptotic approximation to a Gaussian distribution during pyrolysis and its peak value is less than that of a standard Gaussian distribution.According to the conversion ratio vs temperature,activation energy relationships and the thermal mass loss features of humic acids,four and five stages of a general pyrolytic process were found for F-HA and DF-HA,respectively.The chemical reactions for each stage of the pyrolytic process are discussed in detail.(2) The distribution functions of the activation energy of hydrogen generation for F-HA and DF-HA have an asymptotic approximation to a Gaussian distribution during pyrolysis.The activation energy of hydrogen generation increased with an increase in the conversion yields but it also showed staged features.Based on the kinetic characteristics of their generation during pyrolysis their hydrogen generation processes can be divided into five stages,which reflect the different chemical reaction mechanisms.(3) The demineralization of Yimin fusain influences the thermal behavior,kinetics of the pyrolytic processes and the hydrogen generation of humic acid.

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期刊信息
  • 《物理化学学报》
  • 中国科技核心期刊
  • 主管单位:中国科学技术协会
  • 主办单位:北京大学化学与分子工程学院承办
  • 主编:刘忠范
  • 地址:北京大学化学楼
  • 邮编:100871
  • 邮箱:whxb@pku.edu.cn
  • 电话:010-62751724
  • 国际标准刊号:ISSN:1000-6818
  • 国内统一刊号:ISSN:11-1892/O6
  • 邮发代号:82-163
  • 获奖情况:
  • 中文核心期刊
  • 国内外数据库收录:
  • 俄罗斯文摘杂志,美国化学文摘(网络版),荷兰文摘与引文数据库,美国科学引文索引(扩展库),英国科学文摘数据库,日本日本科学技术振兴机构数据库,中国中国科技核心期刊,中国北大核心期刊(2004版),中国北大核心期刊(2008版),中国北大核心期刊(2011版),中国北大核心期刊(2014版),英国英国皇家化学学会文摘,中国北大核心期刊(2000版)
  • 被引量:24781