煤热解过程多环芳烃生成规律研究
摘要
煤利用过程产生的环境污染已经成为煤洁净转化的重要议题,其中煤热加工过程排放的有机污染物特别是多环芳烃(PAHs)类物质,由于其具有“三致”作用,更是近年来关注的热点。煤炭作为世界特别是中国的主要能源,在使用过程中释放出许多此类污染物,使得研究煤的利用过程中PAHs排放具有重要的理论和社会意义。
热解是煤热转化的最基本过程,无论是燃烧、干馏、气化还是液化,都有煤的热解作为其初始和伴随反应,并对后续转化产生重要影响,所以本课题重点是对煤热解过程中多环芳烃排放规律的研究。
本文在充分研究煤的热解机理及影响因素的基础上,对煤热解过程中PAHs生成与排放规律进行了研究。为了避免先用溶剂吸收再分析的传统分析方法中带来的误差,采用了快速热解在线分析方法。快速升温热解仪升温速率最大可达到2×104℃/s,可以进行同一煤样不同热解温度段产生多环芳烃的在线分析。实验收集了国内16种不同变质程度的煤样进行热解,对热解过程中PAHs生成排放从内因和外因两个方面进行了研究。内因主要有挥发份含量、碳含量、氧含量、硫含量、灰分以及煤岩组成;外在因素主要指热解温度和升温速率的影响。得到的主要结论有:煤种对煤热解过程中PAHs的排放影响很大,随着煤中挥发份的提高,PAHs排放量先增大后减少,在高挥发性烟煤阶段生成量最大;随碳含量增加PAHs生成量先增大后减少,烟煤生成量最大;煤中矿物质对PAHs生成有促进作用,随着煤中灰份含量的增大热解生成PAHs量增大;煤中所含的氧和硫含量对PAHs生成也有不同影响;煤岩组成对PAHs热解过程有着重要影响,实验表明煤中惰质组含量越高热解生成PAHs量越大;随热解温度增加,PAHs生成量先增大后减少在800℃出现最大值,PAHs环数分布也随之变化,2～3环PAHs在800℃下生成量最大;4环PAHs在600℃下最高;5～6环PAHs在高温下含量最高;自由基芳构化反应主要在600～800℃下进行,高温下主要发生了缩合反应;随升温速率增加PAHs生成量减少;煤热解PAHs生成来源有煤自身芳烃结构挥发及热解生成自由基高温聚合,且热解过程PAHs主要来自于自由基高温合成而不是煤自身所含芳烃结构。
The environment problems caused by coal utilization have been paid widespread attention. It is very necessary to do some research on the formation, emission and control of PAHs during coal utilization,because trace PAHs is widely distributed , is generally difficult to decompose, is harmful with biological accumulation and three-cause tardy effects including carcinogenesis,aberration, mutation.
Pyrolysis research, in particular, has gained considerable momentum because of its close connection to combustion,gasification and liquefaction.The results of scientific investigations of coal pyrolysis are the indispensable basis for technology in almost all areas of coal utilization. So the present paper focus on the emission of PAHs from coal pyrolysis.
This study was carried out based on the full understanding of the coal pyrolysis process. In order to avoid the error that caused by isolation of particles on filters with subsequent analysis performed, the experiment used flash pyrolysis and Real-time analysis. The pyrolyzer can reach a heating rate as fast as 2×104℃/s and could pyrolyze the same sample at different temperature. PAHs emitted from 16 kinds of different rank Chinese coals during pyrolysis were studied from the internal factors and external factors. The internal factors contains volatile content, carbon content, oxygen content, sulfur content, ash content and maceral. The external factors contain temperature and heating rate. The results show that: the coal type has a remarkable influence on PAHs emission and the high volatile bituminous emit the most PAHs at the same pyrolysis condition. The emission of total PAHs increase with ash content increased. The oxygen and sulfur content has influence on PAHs emission. Maceral components of coal have influence on PAHs emission too, the higher of inertinite content in coal the more PAHs emited. Temperature is an important parameter in coal pyrolysis and with temperatre increased it shows a single peak at 800℃. The PAHs emission decreases with heating rate increasing.
热解是煤热转化的最基本过程,无论是燃烧、干馏、气化还是液化,都有煤的热解作为其初始和伴随反应,并对后续转化产生重要影响,所以本课题重点是对煤热解过程中多环芳烃排放规律的研究。
本文在充分研究煤的热解机理及影响因素的基础上,对煤热解过程中PAHs生成与排放规律进行了研究。为了避免先用溶剂吸收再分析的传统分析方法中带来的误差,采用了快速热解在线分析方法。快速升温热解仪升温速率最大可达到2×104℃/s,可以进行同一煤样不同热解温度段产生多环芳烃的在线分析。实验收集了国内16种不同变质程度的煤样进行热解,对热解过程中PAHs生成排放从内因和外因两个方面进行了研究。内因主要有挥发份含量、碳含量、氧含量、硫含量、灰分以及煤岩组成;外在因素主要指热解温度和升温速率的影响。得到的主要结论有:煤种对煤热解过程中PAHs的排放影响很大,随着煤中挥发份的提高,PAHs排放量先增大后减少,在高挥发性烟煤阶段生成量最大;随碳含量增加PAHs生成量先增大后减少,烟煤生成量最大;煤中矿物质对PAHs生成有促进作用,随着煤中灰份含量的增大热解生成PAHs量增大;煤中所含的氧和硫含量对PAHs生成也有不同影响;煤岩组成对PAHs热解过程有着重要影响,实验表明煤中惰质组含量越高热解生成PAHs量越大;随热解温度增加,PAHs生成量先增大后减少在800℃出现最大值,PAHs环数分布也随之变化,2～3环PAHs在800℃下生成量最大;4环PAHs在600℃下最高;5～6环PAHs在高温下含量最高;自由基芳构化反应主要在600～800℃下进行,高温下主要发生了缩合反应;随升温速率增加PAHs生成量减少;煤热解PAHs生成来源有煤自身芳烃结构挥发及热解生成自由基高温聚合,且热解过程PAHs主要来自于自由基高温合成而不是煤自身所含芳烃结构。
The environment problems caused by coal utilization have been paid widespread attention. It is very necessary to do some research on the formation, emission and control of PAHs during coal utilization,because trace PAHs is widely distributed , is generally difficult to decompose, is harmful with biological accumulation and three-cause tardy effects including carcinogenesis,aberration, mutation.
Pyrolysis research, in particular, has gained considerable momentum because of its close connection to combustion,gasification and liquefaction.The results of scientific investigations of coal pyrolysis are the indispensable basis for technology in almost all areas of coal utilization. So the present paper focus on the emission of PAHs from coal pyrolysis.
This study was carried out based on the full understanding of the coal pyrolysis process. In order to avoid the error that caused by isolation of particles on filters with subsequent analysis performed, the experiment used flash pyrolysis and Real-time analysis. The pyrolyzer can reach a heating rate as fast as 2×104℃/s and could pyrolyze the same sample at different temperature. PAHs emitted from 16 kinds of different rank Chinese coals during pyrolysis were studied from the internal factors and external factors. The internal factors contains volatile content, carbon content, oxygen content, sulfur content, ash content and maceral. The external factors contain temperature and heating rate. The results show that: the coal type has a remarkable influence on PAHs emission and the high volatile bituminous emit the most PAHs at the same pyrolysis condition. The emission of total PAHs increase with ash content increased. The oxygen and sulfur content has influence on PAHs emission. Maceral components of coal have influence on PAHs emission too, the higher of inertinite content in coal the more PAHs emited. Temperature is an important parameter in coal pyrolysis and with temperatre increased it shows a single peak at 800℃. The PAHs emission decreases with heating rate increasing.
引文
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[2]陈文颖,吴宗鑫.用MARKAL模型研究中国未来可持续能源发展战略[J].清华大学学报(自然科学版),2001,41(12):103-106.
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[4]谢克昌.煤的结构与反应性[M].北京:科学出版社,2002:210-215.
[5]虞继舜.煤化学[M].北京:冶金工业出版社,2000:172-177.
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[7] A.Arenillas,F.Rubiera,J.J.Pis,etc . Thermal behaviour during the pyrolysis of low rank perhydrous coals[J].Journal of Analytical and Applied Pyrolysis,2003,69(8):371-385.
[8] H.Hu,Q.Zhou,S Zhu etc.Product distribution and sulfur behavior in coal pyrolysis[J].Fuel Process Technol,2004,85(8-10):849-861.
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[13] A.B Fuertes,J.J Pis,A.J.Perez,etc.Kinetic study of the reaction of a metallurgical coke with CO2[J].Solid State lonics,1990,38(1-2):75-80.
[14] M.A.Telfer,C.A.Heidenreich,D.K.Zhang.Effect of particle size and heating rate on the transformation of sulphur during pyrolysis of a South Australian low-rank coal[J]. Developments in Chemical Engineering and Mineral Processing,1 999,7(3):409-426.
[15] W.Wanzl,D.Bittner.Experiments on pyrolysis behaviour of different coals[J].Fuel
[47] Wang H,Frenklach M.A detailed kinetic modeling study of aromatics formation in laminar premixed acetylene and ethylene flames[J].Combustion and Flame,1997,110:173-221.
[48] J.Thomas Mckinnon , Eleanor Meyer , Jack B. Howard.Infrared Analysis of Flame-Generated PAH Samples[J].Combustion and Flame,1996,105:161-166.
[49] Stephen J.Harris,AnitaM.Weinerand,Richard J.Blini.Kinetic and Thermodynamic issues in the formation of aromatic compounds in flames of aliphatic fuels[J].Combustion and Flame,1988,72:91-109.
[50]晏蓉,原煤及燃后飞灰抽提液中有机物污染物的研究,全国高等学校工程热物理研究会第六届学术会议论文集,武汉,1996,427-430.
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