内蒙褐煤催化解聚过程中催化剂与助剂作用探究
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摘要
在催化解聚概念的基础上,使用格金干馏炉,采用同时添加催化剂和助剂、仅添加催化剂、仅添加助剂的方式,进一步探究了催化剂和助剂对内蒙褐煤催化解聚过程的影响。结果表明,催化剂和助剂在一定程度上促进了气相和液相产物生成,并且对煤的解聚过程产生了干预:仅添加助剂时,煤中的羟基和脂肪侧链的断裂程度加深;仅添加催化剂时,促进了煤中桥键的断裂、脱氢和芳构化;当催化剂和助剂复合添加时,在各方面都体现了仅添加催化剂和仅添加助剂时的叠加结果,但在增加焦油收率方面体现了一定程度的协同效应,更有利于焦油生成,焦油收率由原煤的5. 84%提高到了7. 28%。
Based on the research concept of catalytic depolymerization,using the Gary-King retort,the effect of catalyst and accessory ingredient in the catalytic depolymerization of Inner Mongolia lignite were investigated by adding catalyst with accessory ingredient,only adding catalyst and only adding accessory ingredient.The results showed that the addition of catalyst or accessory ingredient intervened the coal pyrolysis and products yield of gases or liquid phases.When only adding accessory ingredient,the fracture degree of the hydroxyl and fat side chains in the coal is deepened; when only adding catalyst,the fracture,dehydrogenation and aromatization of the bridge bond in coal are promoted; and when adding catalyst with the accessory ingredient,the superposition results of only adding catalyst and only adding accessory ingredient are reflected in all aspects,but the increase in tar yield reflects a certain degree of synergistic effect.Adding catalyst with the accessory ingredient is more beneficial for the formation of tar,which increased from 5.84% of raw coal tar yield to 7.28%.
Based on the research concept of catalytic depolymerization,using the Gary-King retort,the effect of catalyst and accessory ingredient in the catalytic depolymerization of Inner Mongolia lignite were investigated by adding catalyst with accessory ingredient,only adding catalyst and only adding accessory ingredient.The results showed that the addition of catalyst or accessory ingredient intervened the coal pyrolysis and products yield of gases or liquid phases.When only adding accessory ingredient,the fracture degree of the hydroxyl and fat side chains in the coal is deepened; when only adding catalyst,the fracture,dehydrogenation and aromatization of the bridge bond in coal are promoted; and when adding catalyst with the accessory ingredient,the superposition results of only adding catalyst and only adding accessory ingredient are reflected in all aspects,but the increase in tar yield reflects a certain degree of synergistic effect.Adding catalyst with the accessory ingredient is more beneficial for the formation of tar,which increased from 5.84% of raw coal tar yield to 7.28%.
引文
[1]石磊.煤共价键结构在热解过程中的阶段解离研究[D].北京:北京化工大学,2014:10-15.SHI Lei.Study on the cleavage of covalent bonds in coal pyroly sis from various temperature stages[D]. Beijing:Beijing University of Chemical Technology,2014:10-15.
[2]么秋香,樊英杰,冉伟利,等.煤热解催化剂的研究现状及未来发展趋势[J].煤化工,2015,43(1):22-25.ME Qiuxiang,FAN Yingjie,RAN Weili,et al. Research status and development tendency of the coal pyrolysis catalyst[J]. Coal Chemical Industry,2015,43(1):22-25.
[3]胡发亭,张晓静,李培霖.煤焦油加工技术进展及工业化现状[J].洁净煤技术,2011,17(5):31-35.HU Fating,ZHANG Xiaojing,LI Peilin. Development of pro cessing technology and industrialization status of coal tar[J]. Clean Coal Technology,2011,17(5):31-35.
[4]梁丽彤,黄伟,张乾,等.低阶煤催化热解研究现状与进展[J].化工进展,2015,34(10):3617-3622.LIANG Litong,HUANG Wei,ZHANG Qian,et al. Re search status and advances in catalytic pyrolysis of low-rank coal[J]. Chemical Industry and Engineering Progress,2015,34(10):3617-3622.
[5]李爽,陈静升,冯秀燕,等.应用TG-FTIR技术研究黄土庙煤催化热解特性[J].燃料化学学报,2013,41(3):271-276.LI Shuang,CHEN Jingsheng,FENG Xiuyan,et al.Catalytic pyrolysis of Huangtumiao coal:TG-FTIR study[J].Journal of Fuel Chemistry and Technology,2013,41(3):271-276.
[6]赵璞,裴贤丰,王之正.中低温煤焦油加工利用现状研究[J].煤质技术,2016(6):11-16.ZHAO Pu,PEI Xianfeng,WANG Zhizheng.Study on the present situation of medium/low temperature coal tar processing and utilization[J].Goal Quality and Technology,2016(6):11-16.
[7] LIANG L,HUANG W,GAO F,et al.Mild catalytic depolymerization of low rank coals:A novel way to increase tar yield[J]. Rsc Advances,2014,5(4):2493-2503.
[8]梁丽彤.低阶煤催化解聚研究[D].太原:太原理工大学,2016:45-55.LIANG Litong. Research on catalytic depolymerization of lowrank coal[D].Taiyuan:Taiyuan University of Technology,2016:45-55.
[9]高福星,梁丽彤,黄伟,等.催化煤解聚产物分布特性研究[J].煤炭转化,2015,38(2):19-23.GAO Fuxing,LIANG Litong,HUANG Wei,et al. Product dis tribution and characteristics of catalytic depolymerization of coal[J].Coal Conversion,2015,38(2):19-23.
[10]黄晓娟.煤中矿物质对枣庄煤催化解聚的影响[D].太原:太原理工大学,2016.HUANG Xiaojuan.Influence of minerals in coal on the catalytic depolymerization of Zaozhuang coal[D]. Taiyuan:Taiyuan University of Technology,2016
[11] LIU J,ZHANG Q,LIANG L,et al. Catalytic depolymerization of coal char over iron-based catalyst:Potential method for producing high value-added chemicals[J].Fuel,2017:329-333.
[12]黄伟,梁虎珍,梁丽彤,等.一种低阶煤催化解聚增油催化剂[P].中国专利:CN103831113A,2014.
[13]王鹏,文芳,步学朋,等.煤热解特性研究[J].煤炭转化,2005,28(1):8-13.WANG Peng,WEN Fang,BU Xuepeng,et al.Study on the py rolysis characteristics of coal[J].Coal Conversion,2005,28(1):8-13.
[14] SOLOMON P R,FLETCHER T H,PUGMIRE R J.Progress in coal pyrolysis[J].Fuel,1993,72(5):587-597.
[15]石振,成帅,陈兆辉,等.神木烟煤热解产物分布及主要元素的迁移规律[J].过程工程学报,2016,16(5):802-811.SHI Zhen,CHENG Shuai,CHEN Zhaohui,et al. Distribution of products and migration of main elemems during pyrolysis of Shenmu bituminous coal[J].Chinese Journal of Process Engineering,2016,16(5):802-811.
[16]赵丽红,郭慧卿,马青兰.煤热解过程中气态产物分布的研究[J].煤炭转化,2007,30(1):5-9.ZHAO Lihong,GUO Huiqing,MA Qinglan. Study on gaseous products distributions during coal pyrolysis[J]. Coal Conversion,2007,30(1):5-9.
[17]李艳红,赵文波,夏举佩,等.煤焦油分离与精制的研究进展[J].石油化工,2014,43(7):848-855.LI Yanhong,ZHAO Wenbo,XIA Jupei,et al.Progresses in the separation and purification of coal tar[J]. Petrochemical Technology,2014,43(7):848-855.
[18]贾永斌,张守玉.热解和气化过程中焦油裂解的研究[J].煤炭转化,2000,23(4):1-6.JIA Yongbin,ZHANG Shouyu. Study on tar cracking in pyrolysis or gasification process[J].Coal Conversion,2000,23(4):1-6.
[19]陶凤惠,曾鸣,施杰,等.褐煤低温干馏及产物的利用[J].洁净煤技术,2014,21(1):78-82.TAO Fenghui,ZENG Ming,SHI Jie,et al. Lignite low-temperature pyrolysis and utilization of its products[J].Clean Coal Technology,2014,21(1):78-82.
[20]肖瑞华.煤焦油化工学[M].北京:北京冶金工业出版社,2002:25-34.
[21]陈雪,朱来福,刘书林,等.低温煤焦油组分分离及分析[J].燃料与化工,2015,46(4):44-46.CHEN Xue,ZHU Laifu,LIU Shulin,et al. Composition separation and analysis of low temperature coal tar[J]. Fuel&Chemical Processes,2015,46(4):44-46.
[22] IBARRA J,MUOZ E,MOLINER R.FTIR Study of the evolution of coal structure during the coalification process[J]. Organic Geochemistry,1996,24(6):725-735.
[23] LU L,KONG C,SAHAJWALLA V,et al. Char structural ordering during pyrolysis and combustion and its influence on char reactivity[J].Fuel,2002,81(9):1215-1225.
[24]叶俊岭,刘生玉,吕永康.热解温度对半焦生成及其元素组成的影响[J].煤炭转化,2006,29(1):37-40.YE Junling,LIU Shengyu,LYongkang.Influence of pyrolysis temperature on the formation of semicoke and its elemental composition[J].Coal Conversion,2006,29(1):37-40.
[2]么秋香,樊英杰,冉伟利,等.煤热解催化剂的研究现状及未来发展趋势[J].煤化工,2015,43(1):22-25.ME Qiuxiang,FAN Yingjie,RAN Weili,et al. Research status and development tendency of the coal pyrolysis catalyst[J]. Coal Chemical Industry,2015,43(1):22-25.
[3]胡发亭,张晓静,李培霖.煤焦油加工技术进展及工业化现状[J].洁净煤技术,2011,17(5):31-35.HU Fating,ZHANG Xiaojing,LI Peilin. Development of pro cessing technology and industrialization status of coal tar[J]. Clean Coal Technology,2011,17(5):31-35.
[4]梁丽彤,黄伟,张乾,等.低阶煤催化热解研究现状与进展[J].化工进展,2015,34(10):3617-3622.LIANG Litong,HUANG Wei,ZHANG Qian,et al. Re search status and advances in catalytic pyrolysis of low-rank coal[J]. Chemical Industry and Engineering Progress,2015,34(10):3617-3622.
[5]李爽,陈静升,冯秀燕,等.应用TG-FTIR技术研究黄土庙煤催化热解特性[J].燃料化学学报,2013,41(3):271-276.LI Shuang,CHEN Jingsheng,FENG Xiuyan,et al.Catalytic pyrolysis of Huangtumiao coal:TG-FTIR study[J].Journal of Fuel Chemistry and Technology,2013,41(3):271-276.
[6]赵璞,裴贤丰,王之正.中低温煤焦油加工利用现状研究[J].煤质技术,2016(6):11-16.ZHAO Pu,PEI Xianfeng,WANG Zhizheng.Study on the present situation of medium/low temperature coal tar processing and utilization[J].Goal Quality and Technology,2016(6):11-16.
[7] LIANG L,HUANG W,GAO F,et al.Mild catalytic depolymerization of low rank coals:A novel way to increase tar yield[J]. Rsc Advances,2014,5(4):2493-2503.
[8]梁丽彤.低阶煤催化解聚研究[D].太原:太原理工大学,2016:45-55.LIANG Litong. Research on catalytic depolymerization of lowrank coal[D].Taiyuan:Taiyuan University of Technology,2016:45-55.
[9]高福星,梁丽彤,黄伟,等.催化煤解聚产物分布特性研究[J].煤炭转化,2015,38(2):19-23.GAO Fuxing,LIANG Litong,HUANG Wei,et al. Product dis tribution and characteristics of catalytic depolymerization of coal[J].Coal Conversion,2015,38(2):19-23.
[10]黄晓娟.煤中矿物质对枣庄煤催化解聚的影响[D].太原:太原理工大学,2016.HUANG Xiaojuan.Influence of minerals in coal on the catalytic depolymerization of Zaozhuang coal[D]. Taiyuan:Taiyuan University of Technology,2016
[11] LIU J,ZHANG Q,LIANG L,et al. Catalytic depolymerization of coal char over iron-based catalyst:Potential method for producing high value-added chemicals[J].Fuel,2017:329-333.
[12]黄伟,梁虎珍,梁丽彤,等.一种低阶煤催化解聚增油催化剂[P].中国专利:CN103831113A,2014.
[13]王鹏,文芳,步学朋,等.煤热解特性研究[J].煤炭转化,2005,28(1):8-13.WANG Peng,WEN Fang,BU Xuepeng,et al.Study on the py rolysis characteristics of coal[J].Coal Conversion,2005,28(1):8-13.
[14] SOLOMON P R,FLETCHER T H,PUGMIRE R J.Progress in coal pyrolysis[J].Fuel,1993,72(5):587-597.
[15]石振,成帅,陈兆辉,等.神木烟煤热解产物分布及主要元素的迁移规律[J].过程工程学报,2016,16(5):802-811.SHI Zhen,CHENG Shuai,CHEN Zhaohui,et al. Distribution of products and migration of main elemems during pyrolysis of Shenmu bituminous coal[J].Chinese Journal of Process Engineering,2016,16(5):802-811.
[16]赵丽红,郭慧卿,马青兰.煤热解过程中气态产物分布的研究[J].煤炭转化,2007,30(1):5-9.ZHAO Lihong,GUO Huiqing,MA Qinglan. Study on gaseous products distributions during coal pyrolysis[J]. Coal Conversion,2007,30(1):5-9.
[17]李艳红,赵文波,夏举佩,等.煤焦油分离与精制的研究进展[J].石油化工,2014,43(7):848-855.LI Yanhong,ZHAO Wenbo,XIA Jupei,et al.Progresses in the separation and purification of coal tar[J]. Petrochemical Technology,2014,43(7):848-855.
[18]贾永斌,张守玉.热解和气化过程中焦油裂解的研究[J].煤炭转化,2000,23(4):1-6.JIA Yongbin,ZHANG Shouyu. Study on tar cracking in pyrolysis or gasification process[J].Coal Conversion,2000,23(4):1-6.
[19]陶凤惠,曾鸣,施杰,等.褐煤低温干馏及产物的利用[J].洁净煤技术,2014,21(1):78-82.TAO Fenghui,ZENG Ming,SHI Jie,et al. Lignite low-temperature pyrolysis and utilization of its products[J].Clean Coal Technology,2014,21(1):78-82.
[20]肖瑞华.煤焦油化工学[M].北京:北京冶金工业出版社,2002:25-34.
[21]陈雪,朱来福,刘书林,等.低温煤焦油组分分离及分析[J].燃料与化工,2015,46(4):44-46.CHEN Xue,ZHU Laifu,LIU Shulin,et al. Composition separation and analysis of low temperature coal tar[J]. Fuel&Chemical Processes,2015,46(4):44-46.
[22] IBARRA J,MUOZ E,MOLINER R.FTIR Study of the evolution of coal structure during the coalification process[J]. Organic Geochemistry,1996,24(6):725-735.
[23] LU L,KONG C,SAHAJWALLA V,et al. Char structural ordering during pyrolysis and combustion and its influence on char reactivity[J].Fuel,2002,81(9):1215-1225.
[24]叶俊岭,刘生玉,吕永康.热解温度对半焦生成及其元素组成的影响[J].煤炭转化,2006,29(1):37-40.YE Junling,LIU Shengyu,LYongkang.Influence of pyrolysis temperature on the formation of semicoke and its elemental composition[J].Coal Conversion,2006,29(1):37-40.