义马褐煤显微组分酸性含氧基团特征及其抑制甲烷吸附性
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摘要
为探索煤表面酸性含氧基团对低阶煤甲烷吸附行为的影响,采集义马褐煤样品经手选、破碎、研磨、筛分并重液分离富集不同显微组分,借助傅立叶变换红外光谱(FT-IR)测试,Boehm滴定等技术表征褐煤各显微组分富集物酸性含氧基团特征,依据煤化学统计结构解析法推算褐煤基本结构单元萘核,利用重量法等温吸附实验测定褐煤各显微组分富集物及不同酸性含氧基团特征结构化合物的甲烷吸附性.研究发现:义马褐煤酸性含氧基团总量与羧基、酚羟基、内酯基含量最高的显微组分依次为类脂组、腐殖组、惰质组;不同酸性含氧基团对褐煤萘核的抑制甲烷吸附性由大到小依次为羧基,酚羟基,内酯基.其中,羧基相对抑制甲烷吸附量约为内酯基与酚羟基的7倍和3.3倍;在忽略水分条件下考察褐煤显微组分富集物中不同酸性含氧基团对甲烷的吸附行为,结果显示羧基含量增高是造成各显微组分甲烷吸附量降低的主要因素.本研究表明,显微组分含量及煤表面性质是影响褐煤含气性的重要因素,惰质组的高羧酸含量抑制义马褐煤甲烷吸附性效果显著.
To explore effects of acidic oxygen-containing groups on adsorption behavior of lowrank-coal methane,on the basis of collecting and separating maceral components of Yima lignite,acidic oxygen-containing groups of lignite maceral components were characterized by means of FT-IR and Boehm titration.The basic structural unit nuclei was calculated via coal chemical statistical structure analysis,and methane adsorption of the maceral component enrichments and the model compounds with different acidic oxygen-containing groups were determined through weight method.The results show that:the highest total amount of acidic oxy-gen-containing groups and the highest content of carboxyl,phenolic hydroxyl and lactone in the maceral-component enrichments are liptinite,humic and interia.By different acidic oxygencontaining groups,apriority order for methane adsorption inhibition on lignite naphthalene is carboxyl,phenolic hydroxy,lactone;the relative adsorption inhibition of the carboxyl is about7 times and 3.3 times that of the lactone and the hydroxyl.Without considering the water condition,carboxyl content increasing is the main factor resulting in the amount decreasing of methane adsorption capacity of each maceral component.The study reveals that the surface property and content of maceral components are important factors affecting the gas content of lignite,and the higher content of carboxylic acid in Yima lignite inertial group is significant for methane adsorption inhibition.
To explore effects of acidic oxygen-containing groups on adsorption behavior of lowrank-coal methane,on the basis of collecting and separating maceral components of Yima lignite,acidic oxygen-containing groups of lignite maceral components were characterized by means of FT-IR and Boehm titration.The basic structural unit nuclei was calculated via coal chemical statistical structure analysis,and methane adsorption of the maceral component enrichments and the model compounds with different acidic oxygen-containing groups were determined through weight method.The results show that:the highest total amount of acidic oxy-gen-containing groups and the highest content of carboxyl,phenolic hydroxyl and lactone in the maceral-component enrichments are liptinite,humic and interia.By different acidic oxygencontaining groups,apriority order for methane adsorption inhibition on lignite naphthalene is carboxyl,phenolic hydroxy,lactone;the relative adsorption inhibition of the carboxyl is about7 times and 3.3 times that of the lactone and the hydroxyl.Without considering the water condition,carboxyl content increasing is the main factor resulting in the amount decreasing of methane adsorption capacity of each maceral component.The study reveals that the surface property and content of maceral components are important factors affecting the gas content of lignite,and the higher content of carboxylic acid in Yima lignite inertial group is significant for methane adsorption inhibition.
引文
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[19]李岩,王云鹏,赵长毅,等.煤中干酪根在热演化中结构变化的红外光谱研究[J].矿物岩石地球化学通报,2013,32(1):97-101.LI Yan,WANG Yunpeng,ZHAO Changyi,et al.The FTIR study on structure changes of coal kerogen in the maturation process[J].Bulletin of Mineralogy,Petrology and Geochemistry,2013,32(1):97-101.
[20]段旭琴,王祖讷.煤显微组分表面含氧官能团的XPS分析[J].辽宁工程技术大学学报,2010,29(3):498-501.DUAN Xuqin,WANG Zune.XPS analysis of oxygen contained functional group in coal macerals[J].Journal of Liaoning Technical University,2010,29(3):498-501.
[21]LU X,JIN D,WEI S,et al.Competitive adsorption of a binary CO2-CH4 mixture in nanoporous carbons:Effects of edge-functionalization[J].Nanoscale,2015,7(3):1002-1012.
[22]JIN D,LU X,ZHANG M,et al.The adsorption behaviour of CH4 on micro-porous carbons:Effects of surface heterogeneity[J].Physical Chemistry Chemical Physics,2014,16(22):11037-11046.
[23]HAO S,WEN J,YU X,et al.Effect of the surface oxygen groups on methane adsorption on coals[J].Applied Surface Science,2013,264:433-442.
[24]降文萍,张群,李建武.不同实验条件下Langmuir体积随煤级变化机理研究[J].天然气地球科学,2009,20(3):442-445.JIANG Wenping,ZHANG Qun,LI Jianwu.Study on the mechanism of Langmuir capacity with coal ranks on different experimental conditions[J].Natural Gas Geoscience,2009,20(3):442-445.
[25]张锦,张登峰,霍培丽,等.煤基质表面官能团对二氧化碳及甲烷吸附性能作用规律的研究进展[J].化工进展,2017,36(6):1977-1988.ZHANG Jin,ZHANG Dengfeng,HUO Peili,et al.Functional groups on coal matrix surface dependences of carbon dioxide and methane adsorption:A perspective[J].Chemical Industry and Engineering Progress,2017,36(6):1977-1988.
[26]谢克昌.煤的结构与反应性[M].北京:科学出版社,2002:167-171.XIE Kechang.Coal structure and its reactivity[M].Beijing:Science Press,2002:167-171.
[27]汤海燕.胜利褐煤结构的研究及腐植酸分子结构模型的构建[D].徐州:中国矿业大学,2015:64-78.TANG Haiyan.Study on the structure of Shengli lignite and construction of the molecular structure models of the humic acids in Shengli lignite[D].Xuzhou:China University of Mining and Technology,2015:64-78.
[28]贾燕.褐煤结构的实验分析[D].太原:太原理工大学,2002:12-16.JIA Yan.The experimental analysis of brown coal structure[D].Taiyuan:Taiyuan University of Technology,2002:12-16.
[2]郭红玉,符超勇,拜阳,等.生物产气对煤层气可采性指标的影响[J].天然气工业,2017,37(2):46-51.GUO Hongyu,FU Chaoyong,BAI Yang,et al.Influence of biogenic gas production on coalbed methane recoverability parameters[J].Natural Gas Industry,2017,37(2):46-51.
[3]WANG Q Q,LI W,ZHANG D F,et al.Influence of high-pressure CO2,exposure on adsorption kinetics of methane and CO2on coals[J].Journal of Natural Gas Science&Engineering,2016,34:811-822.
[4]WANG Q Q,ZHANG D F,WANG H H,et al.Influence of CO2 exposure on high-pressure methane and CO2adsorption on various rank coals:Implications for CO2sequestration in coal seams[J].Energy&Fuels,2015,29(6):3785-3795.
[5]ZHANG D F,CUI Y J,LIU B,et al.Supercritical pure methane and CO2 adsorption on various rank coals of China:Experiments and modeling[J].Energy&Fuels,2011,25(4):1891-1899.
[6]李国玲,秦志宏,倪中海.煤岩显微组分的性质研究进展[J].辽宁大学学报(自然科学版),2013,40(1):48-55.LI Guoling,QIN Zhihong,NI Zhonghai.Advances in the characteristics of coal macerals[J].Journal of Liaoning University(Natural Sciences Edition),2013,40(1):48-55.
[7]CAI Y,LIU D,PAN Z,et al.Pore structure and its impact on CH4adsorption capacity and flow capability of bituminous and subbituminous coals from northeast China[J].Fuel,2013,103:258-268.
[8]李子文.低阶煤的微观结构特征及其对瓦斯吸附解吸的控制机理研究[D].徐州:中国矿业大学,2015:41-71.LI Ziwen.Study on microstructure characteristics of low rank coal and its control mechanism on gas adsorption/desorption[D].Xuzhou:China University of Mining and Technology,2015:41-71.
[9]王永刚,周剑林,林雄超.低阶煤含氧官能团赋存状态及其对表面性质的影响[J].煤炭科学技术,2013,41(9):182-184.WANG Yonggang,ZHOU Jianlin,LIN Xiongchao.Deposit conditions ofoxygen functional groups in low rank coal and affected to surfaceproperties[J].Coal Science and Technology,2013,41(9):182-184.
[10]段旭琴,王祖讷,孙春宝.神府煤显微组分表面性质研究[J].中国矿业大学学报,2007,36(5):630-635.DUAN Xuqin,WANG Zune,SUN Chunbao.Surface properties of macerals from Shenfu[J].Journal of China University of Mining&Technology,2007,36(5):630-635.
[11]张小兵,郇璇,张航,等.不同煤体结构煤基活性炭微观结构与甲烷吸附性能[J].中国矿业大学学报,2017,46(1):155-161.ZHANG Xiaobing,HUAN Xuan,ZHANG Hang,et al.Microstructure and methane adsorption of coalbased activated carbons with different coal body structures[J].Journal of China University of Mining&Technology,2017,46(1):155-161.
[12]SHAFEEYAN M S,WAN M A W D,HOUSHMAND A,et al.A review on surface modification of activated carbon for carbon dioxide adsorption[J].Journal of Analytical&Applied Pyrolysis,2010,89(2):143-151.
[13]JARAMILLO J,ALVAREZ P M,GOMEZ SERRANO V.Oxidation of activated carbon by dry and wet methods:Surface chemistry and textural modifications[J].Fuel Processing Technology,2010,91(11):1768-1775.
[14]朱学栋,朱子彬,韩崇家,等.煤中含氧官能团的红外光谱定量分析[J].燃料化学学报,1999,27(4):335-339.ZHU Xuedong,ZHU Zibin,HAN Chongjia,et al.Quantitative determination of oxygen-containing functional groups in coal by FTIR spectroscopy[J].Journal of Fuel Chemistry and Technology,1999,27(4):335-339.
[15]余晓露,白帆,李志明.衰减全反射-显微傅立叶变换红外光谱原位分析煤有机显微组分[J].石油实验地质,2012,34(6):664-670.YU Xiaolu,BAI Fan,LI Zhiming.Application of attenuated total reflectance-micro-Fourier transform infrared spectroscopy to in situ study of coal macerals[J].Petroleum Geology&Experiment,2012,34(6):664-670.
[16]ALLAN J,LARTER S R.Aromatic structures in coal maceral extract and kerogens[J].Organic Geochemistry,1984,6:534-545.
[17]韩峰,张衍国,蒙爱红,等.云南褐煤结构的FTIR分析[J].煤炭学报,2014,39(11):2293-2299.HAN Feng,ZHANG Yanguo,MENG Aihong,et al.FTIR analysis of Yunnan lignite[J].Journal of China Coal Society,2014,39(11):2293-2299.
[18]孙旭光,陈建平,郝多虎.塔里木盆地煤显微组分显微傅里叶红外光谱特征及意义[J].北京大学学报(自然科学版),2001,37(6):832-838.SUN Xuguang,CHEN Jianping,HAO Duohu.Micro-FTIR spectroscopy of macerals in coals from the Tarim Basin[J].Acta Scientiarum Naturalium Universitatis Pekinensis,2001,37(6):832-838.
[19]李岩,王云鹏,赵长毅,等.煤中干酪根在热演化中结构变化的红外光谱研究[J].矿物岩石地球化学通报,2013,32(1):97-101.LI Yan,WANG Yunpeng,ZHAO Changyi,et al.The FTIR study on structure changes of coal kerogen in the maturation process[J].Bulletin of Mineralogy,Petrology and Geochemistry,2013,32(1):97-101.
[20]段旭琴,王祖讷.煤显微组分表面含氧官能团的XPS分析[J].辽宁工程技术大学学报,2010,29(3):498-501.DUAN Xuqin,WANG Zune.XPS analysis of oxygen contained functional group in coal macerals[J].Journal of Liaoning Technical University,2010,29(3):498-501.
[21]LU X,JIN D,WEI S,et al.Competitive adsorption of a binary CO2-CH4 mixture in nanoporous carbons:Effects of edge-functionalization[J].Nanoscale,2015,7(3):1002-1012.
[22]JIN D,LU X,ZHANG M,et al.The adsorption behaviour of CH4 on micro-porous carbons:Effects of surface heterogeneity[J].Physical Chemistry Chemical Physics,2014,16(22):11037-11046.
[23]HAO S,WEN J,YU X,et al.Effect of the surface oxygen groups on methane adsorption on coals[J].Applied Surface Science,2013,264:433-442.
[24]降文萍,张群,李建武.不同实验条件下Langmuir体积随煤级变化机理研究[J].天然气地球科学,2009,20(3):442-445.JIANG Wenping,ZHANG Qun,LI Jianwu.Study on the mechanism of Langmuir capacity with coal ranks on different experimental conditions[J].Natural Gas Geoscience,2009,20(3):442-445.
[25]张锦,张登峰,霍培丽,等.煤基质表面官能团对二氧化碳及甲烷吸附性能作用规律的研究进展[J].化工进展,2017,36(6):1977-1988.ZHANG Jin,ZHANG Dengfeng,HUO Peili,et al.Functional groups on coal matrix surface dependences of carbon dioxide and methane adsorption:A perspective[J].Chemical Industry and Engineering Progress,2017,36(6):1977-1988.
[26]谢克昌.煤的结构与反应性[M].北京:科学出版社,2002:167-171.XIE Kechang.Coal structure and its reactivity[M].Beijing:Science Press,2002:167-171.
[27]汤海燕.胜利褐煤结构的研究及腐植酸分子结构模型的构建[D].徐州:中国矿业大学,2015:64-78.TANG Haiyan.Study on the structure of Shengli lignite and construction of the molecular structure models of the humic acids in Shengli lignite[D].Xuzhou:China University of Mining and Technology,2015:64-78.
[28]贾燕.褐煤结构的实验分析[D].太原:太原理工大学,2002:12-16.JIA Yan.The experimental analysis of brown coal structure[D].Taiyuan:Taiyuan University of Technology,2002:12-16.