煤焦油中酚类化合物的分离及其组成结构鉴定研究进展
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摘要
酚类化合物的提取是实现煤焦油高附加值利用的有效途径之一,掌握煤焦油中酚类化合物的分布情况、结构特点有助于高效分离方法的开发。针对煤焦油中粗酚的提取及精制,本文综述了碱液抽提法、溶剂萃取法和新型分离方法 3类粗酚提取方法的研究现状,介绍了粗酚精制的研究进展,并讨论了不同粗酚提取、精制方法之间的优势与不足。系统阐述了光谱法、色谱法及核磁共振法3大类酚类化合物组成结构鉴定方法。探讨了该领域技术的发展趋势,认为酚类的分析鉴定需将多种先进手段结合,多层次、全方位地分析其组成及结构;粗酚的提取可以加快环保高效萃取剂的优选,推动新型萃取法的应用进度;粗酚精制在重点开发间、对甲酚及混合二甲酚高效提纯工艺的同时,加强高级酚提取的研究力度。
The separation of phenolic compounds is one of the effective ways to realize the high value-added utilization of coal tar. The understanding of the distribution of phenolic compounds and their structure characteristics is favorable of the development of efficient separation methods.Aiming at the separation and purification of phenolic compounds,this paper reviewed three kinds of separation methods of phenolic compounds(alkali extraction method,solvent extraction and new methods) and introduced the progress of phenolic compounds purification.The advantages and disadvantages of different separation and purification methods were also compared objectively.Three kinds of identification methods(spectrophotometry,chromatography and nuclear magnetic resonance)were introduced systematically.This paper discussed the development trend of technology in this field,and pointed out that the analysis and identification of phenols needed to combine various advanced methods for analyzing its composition and structure in multi-level and all-round way.The selection of environment friendly and efficient extracting agent could be accelerated to promote the application of new extraction methods.The purification of phenolic compounds should be focused on developing the efficient purification processes ofm/p cresol and mixed cresol,and strengthening the extraction of advanced phenols.
The separation of phenolic compounds is one of the effective ways to realize the high value-added utilization of coal tar. The understanding of the distribution of phenolic compounds and their structure characteristics is favorable of the development of efficient separation methods.Aiming at the separation and purification of phenolic compounds,this paper reviewed three kinds of separation methods of phenolic compounds(alkali extraction method,solvent extraction and new methods) and introduced the progress of phenolic compounds purification.The advantages and disadvantages of different separation and purification methods were also compared objectively.Three kinds of identification methods(spectrophotometry,chromatography and nuclear magnetic resonance)were introduced systematically.This paper discussed the development trend of technology in this field,and pointed out that the analysis and identification of phenols needed to combine various advanced methods for analyzing its composition and structure in multi-level and all-round way.The selection of environment friendly and efficient extracting agent could be accelerated to promote the application of new extraction methods.The purification of phenolic compounds should be focused on developing the efficient purification processes ofm/p cresol and mixed cresol,and strengthening the extraction of advanced phenols.
引文
[1]水恒福,张德祥,张超群.煤焦油分离与精制[M].北京:化学工业出版社,2007.SHUI Hengfu,ZHANG Dexiang,ZHANG Chaoqun.Separation and refining of coal tar[M].Beijing:Chemical Industry Press,2007.
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[3]战风涛,吕志凤,王洛秋,等.催化柴油中的酚类化合物及其对柴油安定性的影响[J].燃料化学学报,2008,28(1):59-62.ZHAN Fengtao,LV Zhifeng,WANG Luoqiu,et al.Identification of phenolic compounds in LCOs and their effects on stability of diesels[J].Journal of Fuel Chemistry and Technology,2000,28(1):59-62.
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[5]王汝成,王宁波,王明峰,等.中低温煤焦油中酚类化合物的柱层析分离[J].煤化工,2013(6):53-56.WANG Rucheng,WANG Ningbo,WANG Mingfeng,et al.Column chromatography isolation of phenolic compounds in the low temperature coal tar[J].Coal Chemical Industry,2013(6):53-56.
[6]葛宜掌,金红.沉淀法回收煤焦油和含酚废水中酚类的研究[J].煤炭学报,1995,20(5):545-550.GE Yizhang,JIN Hong.Recovery of phenols from coal tar and waste water by precipitation[J].Journal of China Coal Society,1995,20(5):545-550.
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[8]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(2):67-75.ZHENG Zhong,YU Yingmin,HU Rang,et al.Separation and utilization of phenolic compounds in Shenmu low temperature coal tar[J].Coal Conversion,2016,39(2):67-75.
[9]包文杰,李永伦,高山松,等.碱盐提取煤加氢液化轻油中的低级酚[J].现代化工,2015,35(6):110-114..BAO Wenjie,LI Yonglun,GAO Shansong,et al.Separation of low-boiling phenol compounds from coal liquefaction light weight oil with alkali salt[J].Modern Chemical Industry,2015,35(6):110-114.
[10]刘巧霞.陕北中低温煤焦油中酚类化合物的抽提研究[D].西安:西北大学,2011.LIU Qiaoxia.Study on extraction phenols of the medium and low temperature coal tar from north Shaanxi[D].Xi’an:Northwest University,2011.
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[14]彭威.离子液体用于油中酚类化合物的萃取研究[D].北京:北京化工大学,2012.PENG Wei.Extraction of phenolic compounds from oils using ionic liquids[D].Beijing:Beijing University of Chemical Technology,2012.
[15]JIAO T,GONG M,ZHUANG X,et al.A new separation method for phenolic compounds from low-temperature coal tar with urea by complex formation[J].Journal of Industrial and Engineering Chemistry,2015,29:344-348.
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[17]蒋胤.结晶法分离间、对甲酚[J].煤化工,1995(1):58-60.JIANG Yin.Separation of meta-and para-cresol by crystallization[J].Coal Chemical Industy,1995(1):58-60.
[18]CONG S,LI X G,WU J,et al.Optimization of parameters for melt crystallization of p-cresol[J].Chinese Journal of Chemical Engineering,2012,20(4):649-653.
[19]SHIAU L D,HUANG C H,LIU K F.Separation of the cresol isomers by stripping crystallization[J].Asia-Pacific Journal of Chemical Engineering,2012,7(s1):26-31.
[20]NEUZIL R W,ROSBACK D H.Process for the separation of cresol isomers:US3969422[P].1976-7-13.
[21]ZINNEN H A.Adsorptive separation of cresol isomers[J].Zeolites,1995,4(15):384.
[22]LEE K R,TAN C S.Separation of m-and p-cresols in compressed propane using modified HZSM-5 pellets[J].Industrial&Engineering Chemistry Research,2000,39:1035-1038.
[23]黄园园,周升,李永伦,等.络合法高效分离煤基粗酚中的间/对甲酚[J].石油化工,2016,45(12):1487-1492.HUANG Yuanyuan,ZHOU Sheng,LI Yonglun,et al.High efficient separation of m/p-cresols in coal-based crude phenols through complexing[J].Petrochemial Technology,2016,45(12):1487-1492.
[24]周银娥,陈爱刚.尿素法分离间、对甲酚工艺的优化[J].江苏化工,1997(25):50-51.ZHOU Yine,CHEN Aigang.The optimization of the separation m-cresol and p-cresol mixture by urea method[J].Jiangsu Chemical Industry,1997(25):50-51.
[25]张超群.煤焦油中酚类组分的提取与分离[D].青岛:中国石油大学(华东),2009.ZHANG Chaoqun.Extraction and separation of the phenolic components from coal tar[D].Qingdao:China University of Petroleum,2009.
[26]宋晓敏,陈源光.间甲酚的分离精制及应用[J].煤炭转化,1998,21(1):91-93.SONG Xiaomin,CHEN Yuanguang.Study on separation and refining and application of m-methyl phenol[J].Coal Conversion,1998,21(1):91-93.
[27]安颖.间甲酚与对甲酚的分离研究[D].天津:天津大学,2004.AN Ying.Study on the separation of m-and p-cresol[D].Tianjin:Tianjin University,2004.
[28]李文凤,王茜,董燕飞.改性Hβ沸石上对甲酚与异丁烯的烷基化反应[J].化学工业与工程,2007,24(3):254-257.LI Wenfeng,WANG Qian,DONG Yanfei,et al.Alkylation of p-cresol with isobutylene over modifiedβzeolite[J].Chemical Industry and Engineering,2007,24(3):254-257.
[29]吴冰,沈健,李会鹏,等.HF/USY分子筛催化合成2-叔丁基对甲酚[J].工业催化,2008,16(5):67-70.WU Bing,SEHN Jian,LI Huipeng,et al.Synthesis of2-t-butyl-p-cresol over supported HF/USY catalyst[J].Industrial Catalysis,2008,16(5):67-70.
[30]王文霞,封超,张秀成.6-叔丁基3-甲基苯酚脱叔丁基制间甲酚[J].精细化工,2012,41(1):62-65.WANG Wenxia,FENG Chao,ZHANG Xiucheng.Dealkylation of6-tert-buty-3-methyl-phenol to m-cresol[J].Petrochemical Technology,2012,41(1):62-65.
[31]OGAN K,KATZ E.Liquid chromatographic separation of alkyl phenols with fluorescence and ultraviolet detection[J].Anal.Chem.,1981,53(2):160-163.
[32]SUN M,CHEN J,DAI X,et al.Controlled separation of low temperature coal tar based on solvent extraction-column chromatography[J].Fuel Processing Technology,2015,136:41-49.
[33]任洪凯,邓文安,李传,等.中/低温煤焦油酚类化合物的组成研究[J].煤炭转化,2013,36(2):67-70.REN Hongkai,DENG Wenan,LI Chuan,et al.Study on the composition of phenolic compounds in middle/low temperature coal tar[J].Coal Conversion,2013,36(2):67-70.
[34]BADAOUI O,MARION C,NADèGE C,et al.Investigating comprehensive two-dimensional gas chromatography conditions to optimize the separation of oxygenated compounds in a direct coal liquefaction middle distillate[J].Journal of Chromatography A,2011,1218(21):3233-3240.
[35]MCGREGOR L A,GAUCHOTTE-LINDSAY C,DAEIDNIAMH N,et al.Multivariate statistical methods for the environmental forensic classification of coal tars from former manufactured gas plants[J].Environmental Science and Technology,2012,46(7):3744-3752.
[36]BHATIA K.Determination of trace phenol in aqueous solution by a queous liquid chromatography[J].Anal.Chem.,1973,45(8):1344-1347.
[37]SCHABRON J F,HURTUBISE R J.Chromatographic and spectrometric methods for the separation,characterization and identification of alkyl phenols in coal-derived solvents[J].Anal.Chem.,1979,51(9):1426-1433.
[38]周心如,沈立阳,叶茹,等.低温煤焦油中酚含量的高效液相色谱快速测定[J].分析试验室,1994,5(13):4-6.ZHOU Xinru,SHEN Liyang,YE Ru,et al.Rapld determination of phenolic in low temperature pyrolysis coal tars by HPLC[J].Chinese Journal of Analysis Laboratory,1994,5(13):4-6.
[39]ZOCCALI M,TRANCHIDA P Q,MONDELLO L.On-line combination of high performance liquid chromatography with comprehensive two-dimensional gas chromatography-triple quadrupole mass spectrometry:a proof of principle study[J].Anal.Chem.,2015,87(3):1911-1918.
[40]宁永成.有机化合物结构鉴定与有机波谱学[M].北京:科学出版社,2001.NING Yongcheng.Identification of organic compounds and organic spectroscopy[M].Beijing:Science Press,2001.
[41]SYLVLA A Farnum,BRUCE W Farnum.Determination of low-rank coal liquefaction light oils by chromatography and nuclear magnetic resonance spectrometry[J].Anal.Chem.,1982,54(8):979-986.
[2]WANG R C,LIU Q X,MA Y X,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.
[3]战风涛,吕志凤,王洛秋,等.催化柴油中的酚类化合物及其对柴油安定性的影响[J].燃料化学学报,2008,28(1):59-62.ZHAN Fengtao,LV Zhifeng,WANG Luoqiu,et al.Identification of phenolic compounds in LCOs and their effects on stability of diesels[J].Journal of Fuel Chemistry and Technology,2000,28(1):59-62.
[4]魏文德.有机化工原料大全(上卷)[M].北京:化学工业出版社,1999.WEI Wende.Organic chemical raw materials(Volume 1)[M].Beijing:Chemical Industry Press,1999.
[5]王汝成,王宁波,王明峰,等.中低温煤焦油中酚类化合物的柱层析分离[J].煤化工,2013(6):53-56.WANG Rucheng,WANG Ningbo,WANG Mingfeng,et al.Column chromatography isolation of phenolic compounds in the low temperature coal tar[J].Coal Chemical Industry,2013(6):53-56.
[6]葛宜掌,金红.沉淀法回收煤焦油和含酚废水中酚类的研究[J].煤炭学报,1995,20(5):545-550.GE Yizhang,JIN Hong.Recovery of phenols from coal tar and waste water by precipitation[J].Journal of China Coal Society,1995,20(5):545-550.
[7]任军哲.榆林煤热解焦油中酚类化合物的提取与动力学研究[D].西安:西北大学,2016.REN Junzhe.Study on process and kinetics of phenolic compounds from coal pyrolysis tar in Yulin[D].Xi’an:Northwest University,2016.
[8]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(2):67-75.ZHENG Zhong,YU Yingmin,HU Rang,et al.Separation and utilization of phenolic compounds in Shenmu low temperature coal tar[J].Coal Conversion,2016,39(2):67-75.
[9]包文杰,李永伦,高山松,等.碱盐提取煤加氢液化轻油中的低级酚[J].现代化工,2015,35(6):110-114..BAO Wenjie,LI Yonglun,GAO Shansong,et al.Separation of low-boiling phenol compounds from coal liquefaction light weight oil with alkali salt[J].Modern Chemical Industry,2015,35(6):110-114.
[10]刘巧霞.陕北中低温煤焦油中酚类化合物的抽提研究[D].西安:西北大学,2011.LIU Qiaoxia.Study on extraction phenols of the medium and low temperature coal tar from north Shaanxi[D].Xi’an:Northwest University,2011.
[11]毛学锋,李文博,高振楠,等.工艺条件对煤液化油中酚类化合物的影响研究[J].煤炭转化,2010,33(1):26-30.MAO Xuefeng,LI Wenbo,GAO Zhennan,et al.Study on the effects of process conditions on phenolic compounds in direct coal liquefaction oils[J].Coal Conversion,2010,33(1):26-30.
[12]庞雁原.MRF煤低温热解酚类化合物特点、生成规律及其合成多功能聚合物助剂的研究[D].北京:煤炭科学研究总院,1993.PANG Yanyuan.Characteristics,generation rule of phenolic compounds from MRF low-temperature pyrolysis and its study on synthesis of multifunctional polymer additives[D].Beijing:Coal Science Research Institute,1993.
[13]赵渊,黄彭,毛学锋,等.一种从煤液化油或煤焦油中提取酚类化合物的方法:102219649[P].2011-10-19.ZHAO Yuan,HUANG Peng,MAO Xuefeng,et al.A separation method for phenolic compounds from coal liquefied oil or coal tar:CN102219649[P].2011-10-19.
[14]彭威.离子液体用于油中酚类化合物的萃取研究[D].北京:北京化工大学,2012.PENG Wei.Extraction of phenolic compounds from oils using ionic liquids[D].Beijing:Beijing University of Chemical Technology,2012.
[15]JIAO T,GONG M,ZHUANG X,et al.A new separation method for phenolic compounds from low-temperature coal tar with urea by complex formation[J].Journal of Industrial and Engineering Chemistry,2015,29:344-348.
[16]庄绪磊.焦油中酚类化合物的分离研究[D].青岛:青岛科技大学,2014.ZHUANG Xulei.Research of separate phenolic compounds from oils[D].Qingdao:Qingdao University of Science and Technology,2014.
[17]蒋胤.结晶法分离间、对甲酚[J].煤化工,1995(1):58-60.JIANG Yin.Separation of meta-and para-cresol by crystallization[J].Coal Chemical Industy,1995(1):58-60.
[18]CONG S,LI X G,WU J,et al.Optimization of parameters for melt crystallization of p-cresol[J].Chinese Journal of Chemical Engineering,2012,20(4):649-653.
[19]SHIAU L D,HUANG C H,LIU K F.Separation of the cresol isomers by stripping crystallization[J].Asia-Pacific Journal of Chemical Engineering,2012,7(s1):26-31.
[20]NEUZIL R W,ROSBACK D H.Process for the separation of cresol isomers:US3969422[P].1976-7-13.
[21]ZINNEN H A.Adsorptive separation of cresol isomers[J].Zeolites,1995,4(15):384.
[22]LEE K R,TAN C S.Separation of m-and p-cresols in compressed propane using modified HZSM-5 pellets[J].Industrial&Engineering Chemistry Research,2000,39:1035-1038.
[23]黄园园,周升,李永伦,等.络合法高效分离煤基粗酚中的间/对甲酚[J].石油化工,2016,45(12):1487-1492.HUANG Yuanyuan,ZHOU Sheng,LI Yonglun,et al.High efficient separation of m/p-cresols in coal-based crude phenols through complexing[J].Petrochemial Technology,2016,45(12):1487-1492.
[24]周银娥,陈爱刚.尿素法分离间、对甲酚工艺的优化[J].江苏化工,1997(25):50-51.ZHOU Yine,CHEN Aigang.The optimization of the separation m-cresol and p-cresol mixture by urea method[J].Jiangsu Chemical Industry,1997(25):50-51.
[25]张超群.煤焦油中酚类组分的提取与分离[D].青岛:中国石油大学(华东),2009.ZHANG Chaoqun.Extraction and separation of the phenolic components from coal tar[D].Qingdao:China University of Petroleum,2009.
[26]宋晓敏,陈源光.间甲酚的分离精制及应用[J].煤炭转化,1998,21(1):91-93.SONG Xiaomin,CHEN Yuanguang.Study on separation and refining and application of m-methyl phenol[J].Coal Conversion,1998,21(1):91-93.
[27]安颖.间甲酚与对甲酚的分离研究[D].天津:天津大学,2004.AN Ying.Study on the separation of m-and p-cresol[D].Tianjin:Tianjin University,2004.
[28]李文凤,王茜,董燕飞.改性Hβ沸石上对甲酚与异丁烯的烷基化反应[J].化学工业与工程,2007,24(3):254-257.LI Wenfeng,WANG Qian,DONG Yanfei,et al.Alkylation of p-cresol with isobutylene over modifiedβzeolite[J].Chemical Industry and Engineering,2007,24(3):254-257.
[29]吴冰,沈健,李会鹏,等.HF/USY分子筛催化合成2-叔丁基对甲酚[J].工业催化,2008,16(5):67-70.WU Bing,SEHN Jian,LI Huipeng,et al.Synthesis of2-t-butyl-p-cresol over supported HF/USY catalyst[J].Industrial Catalysis,2008,16(5):67-70.
[30]王文霞,封超,张秀成.6-叔丁基3-甲基苯酚脱叔丁基制间甲酚[J].精细化工,2012,41(1):62-65.WANG Wenxia,FENG Chao,ZHANG Xiucheng.Dealkylation of6-tert-buty-3-methyl-phenol to m-cresol[J].Petrochemical Technology,2012,41(1):62-65.
[31]OGAN K,KATZ E.Liquid chromatographic separation of alkyl phenols with fluorescence and ultraviolet detection[J].Anal.Chem.,1981,53(2):160-163.
[32]SUN M,CHEN J,DAI X,et al.Controlled separation of low temperature coal tar based on solvent extraction-column chromatography[J].Fuel Processing Technology,2015,136:41-49.
[33]任洪凯,邓文安,李传,等.中/低温煤焦油酚类化合物的组成研究[J].煤炭转化,2013,36(2):67-70.REN Hongkai,DENG Wenan,LI Chuan,et al.Study on the composition of phenolic compounds in middle/low temperature coal tar[J].Coal Conversion,2013,36(2):67-70.
[34]BADAOUI O,MARION C,NADèGE C,et al.Investigating comprehensive two-dimensional gas chromatography conditions to optimize the separation of oxygenated compounds in a direct coal liquefaction middle distillate[J].Journal of Chromatography A,2011,1218(21):3233-3240.
[35]MCGREGOR L A,GAUCHOTTE-LINDSAY C,DAEIDNIAMH N,et al.Multivariate statistical methods for the environmental forensic classification of coal tars from former manufactured gas plants[J].Environmental Science and Technology,2012,46(7):3744-3752.
[36]BHATIA K.Determination of trace phenol in aqueous solution by a queous liquid chromatography[J].Anal.Chem.,1973,45(8):1344-1347.
[37]SCHABRON J F,HURTUBISE R J.Chromatographic and spectrometric methods for the separation,characterization and identification of alkyl phenols in coal-derived solvents[J].Anal.Chem.,1979,51(9):1426-1433.
[38]周心如,沈立阳,叶茹,等.低温煤焦油中酚含量的高效液相色谱快速测定[J].分析试验室,1994,5(13):4-6.ZHOU Xinru,SHEN Liyang,YE Ru,et al.Rapld determination of phenolic in low temperature pyrolysis coal tars by HPLC[J].Chinese Journal of Analysis Laboratory,1994,5(13):4-6.
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