中低温煤焦油化学组成及结构的分子水平表征
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摘要
以内蒙褐煤提质装置生产的中低温煤焦油为原料,研究建立了中低温煤焦油自身结构-组成-性质的分子水平表征方法,从宏观水平描述了中低温煤焦油的物理化学性质,在分子层次上详细研究了中低温煤焦油及其不同馏程、不同性质亚组分的化学组成。首先将中低温煤焦油全馏分进行实沸点蒸馏分离为16个窄馏分并进行性质分析,其次对>180℃重质馏分通过酸碱萃取分离出酸性组分、碱性组分和中性组分,并且中性组分在萃取色谱装置上分离获取6个特征亚组分;利用GC/MS分析了其全馏分、窄馏分及各亚组分的分子结构特征。结果表明,该煤焦油全馏分的水含量为28%,20℃时密度1 003.7 kg/m~3,氧含量为7.4%,<180℃馏分含量为14.24%,<360℃馏分含量为63.4%,属一种典型的中低温煤焦油。中低温煤焦油的<180℃轻质馏分的分子组成以苯、甲苯和二甲苯为主,含有部分小分子烷烃和烯烃。在> 180℃重质馏分中,其酸性组分占27.6%,碱性组分占2.46%,中性组分占69.94%。中性组分中饱和分为33.60%,芳香分为38.70%,胶质占为25.10%,沥青质为2.60%。且中间馏分和重质馏分中含有大量酚类化合物,其分子结构类型以芳烃为主,同时存在长链正构烷烃。中低温煤焦油中含有大量含氧化合物,主要是酚类化合物,以烷基苯酚类为主,在160～280℃相对丰度较高,少部分以酮类化合物存在。
A molecular level characterization method for investigating composition and structure of medium and low temperature coal tar derived from Inner Mongolia lignite upgrading plant has been developed in this paper.The physical and chemical properties of medium and low temperature coal tar was described from macro level.The medium and low temperature coal tar and its chemical composition under different distillation ranges and subcomponent of different natures was investigated from molecular level.Firstly,the whole fraction of medium-low temperature coal tar was separated into 16 narrow fractions by real boiling distillation,and analyzed on their properties.Secondly,the acidic fraction,the alkaline component and the neutral component were separated by acid-base extraction for the >180 ℃ heavy fraction,and the neutral component was separated on the extraction chromatographic apparatus to obtain six characteristic subcomponents.The compositions and molecular structures of full-range fractions,narrow fractions and sub-fractions were analyzed by GC/MS.Results show that the water content of all coal tar fraction is 28%,at 20 ℃,the density is 1003.7 kg/m~3,the oxygen content is 7.4%,and the fraction content( <180 ℃) is 14.24%,and the fraction content( <360 ℃) is 63.4%.This indicates that it is a typical medium and low temperature coal tar.The molecular compositions of light fractions( <180 ℃) mainly comprise benzene,toluene and xylene,with some small molecular alkanes and olefins.In heavy distillate( >180 ℃),acidic compound accounts for 27.6%,basic component 2.46%,neutral component69.94%.In neutral components,Saturation is 33.60%,aromatic 38.70%,gelatine 25.10%,asphaltene 2.60%.The intermediate and heavy fractions also contain a large number of phenolic compounds,with aromatic hydrocarbons as main molecular structure,and long-chain n-alkanes as well.Medium and low temperature coal tar contains a large number of oxygenated compounds,mainly phenolic compounds,alkyl phenols,which are relatively abundant at 160-280 ℃,and also contains a few number of ketones.
A molecular level characterization method for investigating composition and structure of medium and low temperature coal tar derived from Inner Mongolia lignite upgrading plant has been developed in this paper.The physical and chemical properties of medium and low temperature coal tar was described from macro level.The medium and low temperature coal tar and its chemical composition under different distillation ranges and subcomponent of different natures was investigated from molecular level.Firstly,the whole fraction of medium-low temperature coal tar was separated into 16 narrow fractions by real boiling distillation,and analyzed on their properties.Secondly,the acidic fraction,the alkaline component and the neutral component were separated by acid-base extraction for the >180 ℃ heavy fraction,and the neutral component was separated on the extraction chromatographic apparatus to obtain six characteristic subcomponents.The compositions and molecular structures of full-range fractions,narrow fractions and sub-fractions were analyzed by GC/MS.Results show that the water content of all coal tar fraction is 28%,at 20 ℃,the density is 1003.7 kg/m~3,the oxygen content is 7.4%,and the fraction content( <180 ℃) is 14.24%,and the fraction content( <360 ℃) is 63.4%.This indicates that it is a typical medium and low temperature coal tar.The molecular compositions of light fractions( <180 ℃) mainly comprise benzene,toluene and xylene,with some small molecular alkanes and olefins.In heavy distillate( >180 ℃),acidic compound accounts for 27.6%,basic component 2.46%,neutral component69.94%.In neutral components,Saturation is 33.60%,aromatic 38.70%,gelatine 25.10%,asphaltene 2.60%.The intermediate and heavy fractions also contain a large number of phenolic compounds,with aromatic hydrocarbons as main molecular structure,and long-chain n-alkanes as well.Medium and low temperature coal tar contains a large number of oxygenated compounds,mainly phenolic compounds,alkyl phenols,which are relatively abundant at 160-280 ℃,and also contains a few number of ketones.
引文
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[15]石振晶,方梦祥,唐巍,等.多联产煤焦油加氢制取汽柴油试验研究[J].煤炭学报,2014,39(S1):219-224.SHI Zhenjing,FANG Mengxiang,TANG Wei,et al.Hydrofining of wide range distillate derived from muti-generation coal tar[J].Journal of China Coal Society,2014,39(S1):219-224.
[16]姜广策,张生娟,王永刚,等.低温煤焦油中特定芳烃组分的选择性分离[J].化工学报,2015,66(6):2131-2138.JIANG Guangce,ZHANG Shengjuan,WANG Yonggang,et al.Selective separation of aromatic hydrocarbons from low temperature coal tar[J].CIESC Journal,2015,66(6):2131-2138.
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[18]ANCHEYTA J,CENTENO G,TREJO F,et al.Extraction and characterization of asphaltenes from different crude oils and solvents[J].Energy&Fuels,2002,16:1121-1127.
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[20]裴亮军,李冬,袁扬,等.不同正构烷烃溶剂沉淀中低温煤焦油沥青质的结构组成变化规律[J].化工进展,2017,36(6):2101-2108.PEI Liangjun,LI Dong,YUAN Yang,et al.Composition and structural changes of low temperature coal tar asphaltenes precipitated in different n-alkane solvents[J].Chemical Industry and Engineering Progress,2017,36(6):2101-2108.
[21]孙智慧,柴晓华,张卫红,等.中低温煤焦油加氢过程中沥青质组成与性质[J].化学反应工程与工艺,2016,32(6):547-552.SUN Zhihui,CHAI Xiaohua,ZHANG Weihong,et al.The compositions and properties of asphaltene from the medium and low temperature coal tar during hydrogenation process[J].Chemical Reaction Engineering and Technology,2016,32(6):547-552.
[22]郑仲,于英民,胡让,等.神木中低温煤焦油酚类物质的分离与利用[J].煤炭转化,2016,39(1):67-70.ZHENG Zhong,YU Yingmin,HU Rang,et al.Separation and utilizaition of phenolic compounds in shenmu Low-temperature coal tar[J].Coal Conversion,2016,39(1):67-70.
[23]史权,张霖宙,赵锁奇,等.炼化分子管理技术:概念与理论基础[J].石油科学通报,2016,1(2):270-278.SHI Quan,ZHANG Linzhou,ZHAO Suoqi,et al.Molecular management for petroleum refining:concepts and fundamentals[J].Petroleum Science Bulletin,2016,1(2):270-278.
[24]吴青.石油分子工程及其管理的研究与应用(Ⅰ)[J].炼油技术与工程,2017,47(1):1-9.WU Qing.Molecular management for petroleum refining:Concepts and fundamentals research on molecular engineering and molecular management for petroleum and its applications(PartⅠ)[J].Petroleum refining Engineering,2017,47(1):1-9.
[25]田松柏,龙军,李长秀,等.石油轻馏分的分子水平表征技术研究进展[J].石油学报(石油加工),2017,33(4):595-603.TIAN Songbai,LONG Jun,LI Changxiu,et al.Research advance on analytical techniques of the petroleum light fractions at the molecular level[J].Acta Petrolei Sinica(Petroleum Processing Section),2017,33(4):595-603.
[26]田松柏,龙军,刘泽龙,等.分子水平重油表征技术开发及应用[J].石油学报(石油加工),2015,31(2):282-291.TIAN Songbai,LONG Jun,LIU Zelong,et al.Development and application of analytical techniques on heavy oil at the molecular level[J].Acta Petrolei Sinica(Petroleum Processing Section),2015,31(2):282-291.
[2]李振宇,黄格省.推动我国能源生产革命的途径分析[J].化工进展,2015,34(10):3521-3528.LI Zhenyu,HUANG Gesheng.Analysis on ways to promote energy production revolution in China[J].Chemical Industry and Engineering Progress,2015,34(10):3521-3528.
[3]丁郡瑜.中国煤制油产业现状与发展环境分析[J].国际石油经济,2017,25(4):45-49.DING Junyu.Status and development environment of China’s CTL industry[J].International Petroleum Economics,2017,25(4):45-49.
[4]王汝成,孙鸣,刘巧霞,等.陕北中低温煤焦油中酚类化合物的提取与GC/MS分析[J].煤炭学报,2011,36(4):664-669.WANG Rucheng,SUN Ming,LIU Qiaoxia,et al.Extraction and GC/MS analysis of phenolic compounds in low temperature coal tar from Northern Shaanxi[J].Journal of China Coal Society,2011,36(4):664-669.
[5]孙智慧,李稳宏,马海霞,等.中低温煤焦油重组分分离与表征[J].煤炭学报,2015,40(9):2187-2192.SUN Zhihui,LI Wenhong,MA Haixia,et al.Separation and characterization of middle and low temperature coal tar heavy fraction[J].Journal of China Coal Society,2015,40(9):2187-2192.
[6]范建锋,张忠清,姚春雷,等.中温煤焦油加氢生产清洁燃料油试验研究[J].煤炭学报,2013,38(10):1868-1872.FAN Jianfeng,ZHANG Zhongqing,YAO Chunlei,et al.Study on hydrogenation of medium temperature coal tar to clean fuel[J].Journal of China Coal Society,2013,38(10):1868-1872.
[7]史强,张忠孝,曹先常,等.高温煤焦油黏温特性的测定与分析[J].煤炭学报,2014,39(11):2335-2339.SHI Qiang,ZHANG Zhongxiao,CAO Xianchang,et al.Measuring and analyzing on viscosity-temperature characteristic of high temperature coal tar[J].Journal of China Coal Society,2014,39(11):2335-2339.
[8]邓文安,孔振伟,李传,等.高温煤焦油中的固体颗粒对其临氢热反应生焦的影响[J].煤炭学报,2017,42(12):3286-3291.DENG Wen’an,KONG Zhenwei,LI Chuan,et al.Effect of solid particles in high temperature coal tar on coke formation in thermal reaction at hydrogen atmosphere[J].Journal of China Coal Society,2017,42(12):3286-3291.
[9]刘志云.云南解化集团鲁奇法中低温煤焦油的组成分析[J].云南大学学报(自然科学版),2009,31(6):608-615.LIU Zhiyun.Composition analysis of moderate-low temperature coal tar produced with Lurgi method by Yunnan Jiehua Company[J].Journal of Yunnan University,2009,31(6):608-615.
[10]高玉安.煤焦油加氢技术在鲁奇气化工艺上的应用[J].广东化工,2012,39(6):112-113.GAO Yun’an.The application of coal tar hydrogenation on the lurgi gasifier technology[J].Guangdong Chemical Industry,2012,39(6):112-113.
[11]王芳,曾玺,孙延林,等.两段流化床中半焦催化脱除焦油特性[J].化工学报,2017,68(10):3762-3769.WANG Fang,ZENG Xi,SUN Yanlin,et al.Characteristics of char catalytic reforming of tar in two-stage fluidized bed[J].Journal of Chemical Industry and Engineering(China),2017,68(10):3762-3769.
[12]毕继诚,曲旋,严帅,等.一种煤催化加氢气化生产甲烷和轻质焦油的方法[P].中国专利:201710221463.4,2017.
[13]高晋生.煤的热解、炼焦和煤焦油加工[M].北京:化学工业出版社,2010.
[14]张晓静.中低温煤焦油加氢技术[J].煤炭学报,2011,36(5):840-844.ZHANG Xiaojing.Hydrogenating process for coal tar from midlow-temperature coal carbonization[J].Journal of China Coal Society,2011,36(5):840-844.
[15]石振晶,方梦祥,唐巍,等.多联产煤焦油加氢制取汽柴油试验研究[J].煤炭学报,2014,39(S1):219-224.SHI Zhenjing,FANG Mengxiang,TANG Wei,et al.Hydrofining of wide range distillate derived from muti-generation coal tar[J].Journal of China Coal Society,2014,39(S1):219-224.
[16]姜广策,张生娟,王永刚,等.低温煤焦油中特定芳烃组分的选择性分离[J].化工学报,2015,66(6):2131-2138.JIANG Guangce,ZHANG Shengjuan,WANG Yonggang,et al.Selective separation of aromatic hydrocarbons from low temperature coal tar[J].CIESC Journal,2015,66(6):2131-2138.
[17]邓文安,郭瑞龙,李传,等.中/低温煤焦油悬浮床加氢前后的组成变化[J].煤炭学报,2016,41(S1):235-240.DENG Wen’an,GUO Ruilong,LI Chuan,et al.Composition change of medium and low temperature coal tar before and after the slurrybed hydrocracking[J].Journal of China Coal Society,2016,41(S1):235-240.
[18]ANCHEYTA J,CENTENO G,TREJO F,et al.Extraction and characterization of asphaltenes from different crude oils and solvents[J].Energy&Fuels,2002,16:1121-1127.
[19]孙智慧,马海霞,李冬,等.中低温煤焦油加氢前后沥青质组成和结构变化[J].煤炭学报,2014,39(7):1366-1371.SUN Zhihui,MA Haixia,LI Dong,et al.Composition and structure changes of asphaltenes from medium and low temperature coal tar before and after hydrotreating[J].Journal of China Coal Society,2014,39(7):1366-1371.
[20]裴亮军,李冬,袁扬,等.不同正构烷烃溶剂沉淀中低温煤焦油沥青质的结构组成变化规律[J].化工进展,2017,36(6):2101-2108.PEI Liangjun,LI Dong,YUAN Yang,et al.Composition and structural changes of low temperature coal tar asphaltenes precipitated in different n-alkane solvents[J].Chemical Industry and Engineering Progress,2017,36(6):2101-2108.
[21]孙智慧,柴晓华,张卫红,等.中低温煤焦油加氢过程中沥青质组成与性质[J].化学反应工程与工艺,2016,32(6):547-552.SUN Zhihui,CHAI Xiaohua,ZHANG Weihong,et al.The compositions and properties of asphaltene from the medium and low temperature coal tar during hydrogenation process[J].Chemical Reaction Engineering and Technology,2016,32(6):547-552.
[22]郑仲,于英民,胡让,等.神木中低温煤焦油酚类物质的分离与利用[J].煤炭转化,2016,39(1):67-70.ZHENG Zhong,YU Yingmin,HU Rang,et al.Separation and utilizaition of phenolic compounds in shenmu Low-temperature coal tar[J].Coal Conversion,2016,39(1):67-70.
[23]史权,张霖宙,赵锁奇,等.炼化分子管理技术:概念与理论基础[J].石油科学通报,2016,1(2):270-278.SHI Quan,ZHANG Linzhou,ZHAO Suoqi,et al.Molecular management for petroleum refining:concepts and fundamentals[J].Petroleum Science Bulletin,2016,1(2):270-278.
[24]吴青.石油分子工程及其管理的研究与应用(Ⅰ)[J].炼油技术与工程,2017,47(1):1-9.WU Qing.Molecular management for petroleum refining:Concepts and fundamentals research on molecular engineering and molecular management for petroleum and its applications(PartⅠ)[J].Petroleum refining Engineering,2017,47(1):1-9.
[25]田松柏,龙军,李长秀,等.石油轻馏分的分子水平表征技术研究进展[J].石油学报(石油加工),2017,33(4):595-603.TIAN Songbai,LONG Jun,LI Changxiu,et al.Research advance on analytical techniques of the petroleum light fractions at the molecular level[J].Acta Petrolei Sinica(Petroleum Processing Section),2017,33(4):595-603.
[26]田松柏,龙军,刘泽龙,等.分子水平重油表征技术开发及应用[J].石油学报(石油加工),2015,31(2):282-291.TIAN Songbai,LONG Jun,LIU Zelong,et al.Development and application of analytical techniques on heavy oil at the molecular level[J].Acta Petrolei Sinica(Petroleum Processing Section),2015,31(2):282-291.