气流床气化炉的原料反应性评价、过程强化及环境影响
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摘要
"富煤、贫油、少气"的能源赋存特点决定了在相当长的时期内我国煤化工与石油化工相互依存、互为补充的必要性,发展煤化工是发挥我国煤炭资源优势、降低石油对外依存度、保障我国能源安全的重要途径。论文首先对气流床气化炉的原料煤反应活性评价方法做了综述性分析,着重阐述了煤在气流床气化炉内高温、高压环境下组成、结构及性质的变化规律,并深入探讨了工艺强化带来的新的环境问题。结果表明,现有的评价方法难以真实反映出原料性质是否与气流床气化工艺相匹配,有必要对化工生产过程中气流床气化炉内的生产环境进行模拟,建立起合适的原料性质评价体系,重点探究对生产过程影响最深的气化反应活性;对气化工艺参数的强化是有限度的,一味的强化无益于化工生产,寻找工艺和技术经济指标的最优点是工艺强化的研究方向;高温、高压的气化条件下煤中的大分子有机物大多分解,使得酚类、焦油、COD、BOD等传统污染物含量大幅下降,但煤中部分微量元素在高温高压下易挥发、易活化特征以及现代煤化工规模利用煤的累积效益,使得煤中微量有害元素或造成不可忽视的环境影响,其中以Hg、As等微量元素造成的危害最大。为气流床气化工艺寻求合适原料的评价体系、寻求过程强化的限度、对新型污染源的污染进行调研并建立可能的防治方法是现代煤化工进一步发展必须解决的瓶颈问题。
China's fossil fuel reserves can be characterized as rich in coal but deficient in oil and natural gas.Thus,it is understandable that there will exist an interdependence and complementarity between coal chemical industry and petrochemical industry in China for a long time,because development and application of modern coal chemical technology is an important way to cut down the dependence on imported oil and to guarantee the energy security of China.In this paper a literature survey on evaluation methods of coal reactivity was firstly presented,in which special attention was paid to the changes of composition,structure and properties of coal under high temperature and pressure in entrained-flow gasifier.Then the potential pollution issues caused by intensification of coal gasification process were discussed in depth.The results show that the existing approaches to assessment of coal reactivity are not capable of predict accurately whether the feed coal properties match the demand of entrained-flow gasification technology.As a result,before a suitable evaluation method of feed coal reactivity is established,it is necessary to find a way or provide an apparatus to simulate the production conditions in the commercial entrained-flow gasifier.It is not limitless as concerned as intensification of gasification process,because the economical aspect is not always enhanced with the increase of extent of process intensification,so the process enhancement should be directed to balance the technological and economic indices.Under high temperature and pressure conditions of entrained-flow gasification,almost all macromolecular organic compounds in coal are decomposed,resulting in the great decrease of the content of phenols,tar,COD,BOD and other traditional pollutants.Meanwhile,some trace hazardous elements in coal are volatile and easy to be activated under high temperature and pressure,which may give rise to potential environmental issues for this hazardous trace elements will accumulate in environment upon the consumption of coal on a large scale in modern chemical industry. Among them,Hg,As and other trace elements are mostly harmful to the environment.Therefore,searching for a practicable and more accurate evaluation method of feed coal for entrained-flow gasification process,exploring the limits of process enhancement,as well as investigating the environmental impact of harmful trace elements in coal and establishing possible prevention methods,are the bottlenecks that must be solved in the further development of modern coal chemical industry.
China's fossil fuel reserves can be characterized as rich in coal but deficient in oil and natural gas.Thus,it is understandable that there will exist an interdependence and complementarity between coal chemical industry and petrochemical industry in China for a long time,because development and application of modern coal chemical technology is an important way to cut down the dependence on imported oil and to guarantee the energy security of China.In this paper a literature survey on evaluation methods of coal reactivity was firstly presented,in which special attention was paid to the changes of composition,structure and properties of coal under high temperature and pressure in entrained-flow gasifier.Then the potential pollution issues caused by intensification of coal gasification process were discussed in depth.The results show that the existing approaches to assessment of coal reactivity are not capable of predict accurately whether the feed coal properties match the demand of entrained-flow gasification technology.As a result,before a suitable evaluation method of feed coal reactivity is established,it is necessary to find a way or provide an apparatus to simulate the production conditions in the commercial entrained-flow gasifier.It is not limitless as concerned as intensification of gasification process,because the economical aspect is not always enhanced with the increase of extent of process intensification,so the process enhancement should be directed to balance the technological and economic indices.Under high temperature and pressure conditions of entrained-flow gasification,almost all macromolecular organic compounds in coal are decomposed,resulting in the great decrease of the content of phenols,tar,COD,BOD and other traditional pollutants.Meanwhile,some trace hazardous elements in coal are volatile and easy to be activated under high temperature and pressure,which may give rise to potential environmental issues for this hazardous trace elements will accumulate in environment upon the consumption of coal on a large scale in modern chemical industry. Among them,Hg,As and other trace elements are mostly harmful to the environment.Therefore,searching for a practicable and more accurate evaluation method of feed coal for entrained-flow gasification process,exploring the limits of process enhancement,as well as investigating the environmental impact of harmful trace elements in coal and establishing possible prevention methods,are the bottlenecks that must be solved in the further development of modern coal chemical industry.
引文
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[2]钱卫.油页岩资源勘探开发现状及前景分析[J].煤炭加工与综合利用,2014(6):26-30.
[3]国家统计局能源司.中国能源统计年鉴2016[M].北京:中国统计出版社,2016:58-92.
[4] LI J,HU S.History and future of the coal and coal chemical indus-try in China[J].Resources,Conservation&Recycling,2017,124:13-24.
[5] XIONG R,WEI C.Current status and technology trends of zero liq-uid discharge at coal chemical industry in China[J]. Journal ofWater Process Engineering.2017,19:346-351.
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[7]梁鼎成,杨芊.煤化工过程强化保障能源安全的可行性分析[J].煤炭加工与综合利用,2018(8):11-13.LIANG Dingcheng,Yang Qian.The feasibility analysis of strengthe-ning energy security in the process of the coal-to-chemicals[J].Coal Process&Comprehensive Utilization,2018(8):11-13.
[8]汪寿建.现代煤气化技术发展趋势及应用综述[J].化工进展,2016,35(3):653-664.WANG Shoujian.Development and application of modern coal gasi-fication technology[J]. Chemical Industry and Engineering Pro-gress,2016,35(3):653-664.
[9]黄于益,何璐,解强.煤(焦)气化反应活性评价研究进展[J].煤炭转化,2013,36(4):84-89.HUANG Yuyi,HE Lu,XIE Qiang.Evaluation of coal/char gasifica-tion reactivity[J].Coal Conversion,2013,36(4):84-89.
[10] IRFAN M F,USMAN M R,KUSAKABE K. Coal gasification inCO2atmosphere and its kinetics since 1948:A brief review[J].Energy,2011,36(1):12-40.
[11]顾菁,李莉,吴诗勇,等.程序升温热重法研究神府高温煤焦-CO2气化反应性[J].华东理工大学学报(自然科学版),2007,33(3):354-358.GU Jing,LI Li,WU Shiyong,et al. Measurement of CO2gasifica-tion reactivity for high temperature pyrolyzed coal chars by tem-perature-programmed thermogravimetry[J].Journal of East ChinaUniversity of Science and Technology(Natural Science Edition),2007,33(3):354-358.
[12] ZHANG Jiawei,ZONG Zhimin,WANG Taoxia,et al.Reactivitiesof Shenfu chars toward gasification with carbon dioxide[J]. Jour-nal of China University of Mining&Technology,2007,17(2):197-200.
[13] WU Y,WU S,GU J,et al.Differences in physical properties andCO2gasification reactivity between coal char and petroleum coke[J].Process Safety and Environmental Protection,2009,87(5):323-330.
[14] BEAMISH B B,SHAW K J,RODGERS K A,et al.Thermogravim-etric determination of the carbon dioxide reactivity of char fromsome New Zealand coals and its association with the inorganic ge-ochemistry of the parent coal[J]. Fuel Processing Technology,1998,53(3):243-253.
[15]黄于益,解强.气流床煤气化条件下煤(焦)气化反应性评价[J].洁净煤技术,2018,24(1):85-89.HUANG Yuyi,XIE Qiang.Evaluation of coal/char gasification re-activity under condition of entrained flow coal gasification[J].Clean Coal Technology,2018,24(1):85-89.
[16] WALL T F,LIU G,WU H,et al.The effects of pressure on coalreactions during pulverised coal combustion and gasification[J].Progress in Energy and Combustion Science,2002,28(5):405-433.
[17] JAYARAMAN K,GOKALP I,BOSTYN S.High ash coal pyrolysisat different heating rates to analyze its char structure,kinetics andevolved species[J]. Journal of Analytical and Applied Pyrolysis,2015,113:426-433.
[18]任立伟,魏蕊娣,王建森.影响煤气化反应性的关键因素[J].煤炭技术,2014(8):282-284.REN Liwei,WEI Ruidi,WANG Jiansen.Key factors affecting gasi-fication reactivity of coals[J]. Coal Technology,2014(8):282-284.
[19]温雨鑫.高升温速率和压力条件下的煤热解和气化特性研究[D].北京:中国科学院工程热物理研究所,2013.
[20]杨海平,陈汉平,鞠付栋,等.热解条件及煤种对煤焦气化活性的影响[J].中国电机工程学报,2009,29(2):30-34.YANG Haiping,CHEN Hanping,JU Fudong,et al. Influence ofpyrolysis condition and coal type on gasification reactivity of char-coal[J].Proceedings of the CSEE,2009,29(2):30-34.
[21] FLETCHER T H. Swelling properties of coal chars during rapidpyrolysis and combustion[J].Fuel,1993,72(11):1485-1495.
[22]李乾军,章名耀,蒋斌.温度和压力对加压喷动流化床煤部分气化的影响[J].锅炉技术,2010(4):10-13.LI Qianjun,ZHANG Mmingyao,JIANG Bin. Effect of temperatureand pressure on coal gasification in a pressurized spout-fluid bed[J].Boiler Technology,2010(4):10-13.
[23]于遵宏,王辅臣.煤炭气化技术[M].北京:化学工业出版社,2010.
[24] MEGARITIS A,MESSENBOCK R C,CHATZAKIS I N,et al.High-pressure pyrolysis and CO2-gasification of coal macer-al concentrates:Conversions and char combustion reactivities[J].Fuel,1999,78(8):871-882.
[25] LEE C W,JENKINS R G,SCHOBERT H H.Structure and reac-tivity of char from elevated pressure pyrolysis of Illinois No.6 bitu-minous coal[J].Energy&Fuels,2002,6(1):40-47.
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