基于Diels-Alder化学合成煤基高能量密度燃料的模型物反应研究
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摘要
选取基于煤基油中轻质芳烃为前驱体化学合成高能量密度燃料的工艺过程为研究对象,利用轻质芳烃模型化合物,研究了其Diels-Alde化学合成高能量密度燃料过程的反应机理与催化原理。结果表明,在分子筛催化剂作用下,以苯、甲苯、二甲苯和四氢萘等芳烃为前驱体可与降冰片烯发生Diels-Alde化学合成,生成具有多个封闭环平面组成的立体分子构型的高能量密度燃料。其转化率分别为85.2%,93.1%,99.0%和98.3%,选择性分别为95.2%,93.5%,95.5%和15.3%,轻质单环芳烃(BTX)具有优异的选择性和反应性;MCM-22催化剂因具有较大的孔结构和适度的酸性,其反应活性高于ZSM-5,SAPO-34和ZSM-35催化剂;增加反应时间和升高反应温度均有利于Diels-Alder合成反应。通过轻质芳烃模型物化学合成制备的高能量密度燃料具有较高的密度和能量密度,分别为0.941 8 g/cm3和43.79 MJ/L,远高于石油基和煤基喷气燃料。煤基石脑油经过催化重整后,可得到富集轻质芳烃组分,其单环芳烃(BTX、苯、甲苯、二甲苯)含量高达71.05%,另外,仍可通过柱层析或萃取精馏等先进的分离富集技术,进一步提高轻质芳烃组分富集度。因此,以煤基石脑油为起始原料,通过催化重整或柱层析分离后,得到的富集轻质芳烃组分完全可作为前驱体化学合成真实体系下的煤基高能量密度燃料。
The process of Chemical Synthesis of High Energy Density Fuel based on light aromatics from coal-derived oil was investigated.Using light aromatic hydrocarbon model compounds,the reaction mechanism and catalytic principle of Diels-Alde chemical synthesis of high energy density fuel were studied.The results show that aromatics such as benzene,toluene,xylene and tetralin as precursors can be synthesized by Diels-Alder reaction with norbornene over Zeolite Catalyst.High energy density fuel with a stereoscopic configuration of multiple closed ring planes was generated.The conversion rates were 85.2%,93.1%,99% and 98.3%,respectively,and the selectivity was 95.2%,93.5%,95.5%and 15.3% respectively.Thus BTX-aromatics has excellent selectivity and reactivity.MCM-22 catalyst has larger pore structure and moderate acidity,and its reactive activity is higher than that of ZSM-5,SAPO-34 and ZSM-35 catalysts.The increases of reaction time and high temperature are favorable to the synthesis of Diels-Alder reaction.The high energy density fuel produced by the chemical synthesis of light aromatic model compounds has higher density and energy density,and the density is 0.941 8 g/cm3 and energy density is 43.79 MJ/L,respectively,which are much higher than those of petroleum-based and coal-based jet fuels.After the catalytic reformation of coal based naphtha,the concentration of light aromatic hydrocarbons can be obtained.The content of BTX,benzene,toluene and xylene is up to 71.05%.In addition,the enrichment of light aromatic hydrocarbons can be further improved by the advanced separation and enrichment techniques such as column chromatography or extractive distillation.Therefore,using the coal-based Naphtha as a starting material,after the catalytic reformation or column chromatography separation,the enriched light aromatic hydrocarbon components can be used as the precursor of coal-based high energy density fuel based on Diels-Alder Chemical Synthesis.
The process of Chemical Synthesis of High Energy Density Fuel based on light aromatics from coal-derived oil was investigated.Using light aromatic hydrocarbon model compounds,the reaction mechanism and catalytic principle of Diels-Alde chemical synthesis of high energy density fuel were studied.The results show that aromatics such as benzene,toluene,xylene and tetralin as precursors can be synthesized by Diels-Alder reaction with norbornene over Zeolite Catalyst.High energy density fuel with a stereoscopic configuration of multiple closed ring planes was generated.The conversion rates were 85.2%,93.1%,99% and 98.3%,respectively,and the selectivity was 95.2%,93.5%,95.5%and 15.3% respectively.Thus BTX-aromatics has excellent selectivity and reactivity.MCM-22 catalyst has larger pore structure and moderate acidity,and its reactive activity is higher than that of ZSM-5,SAPO-34 and ZSM-35 catalysts.The increases of reaction time and high temperature are favorable to the synthesis of Diels-Alder reaction.The high energy density fuel produced by the chemical synthesis of light aromatic model compounds has higher density and energy density,and the density is 0.941 8 g/cm3 and energy density is 43.79 MJ/L,respectively,which are much higher than those of petroleum-based and coal-based jet fuels.After the catalytic reformation of coal based naphtha,the concentration of light aromatic hydrocarbons can be obtained.The content of BTX,benzene,toluene and xylene is up to 71.05%.In addition,the enrichment of light aromatic hydrocarbons can be further improved by the advanced separation and enrichment techniques such as column chromatography or extractive distillation.Therefore,using the coal-based Naphtha as a starting material,after the catalytic reformation or column chromatography separation,the enriched light aromatic hydrocarbon components can be used as the precursor of coal-based high energy density fuel based on Diels-Alder Chemical Synthesis.
引文
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[13]FENG R,ZOU J,ZHANG X,et al.Theoretical study on cyclopropanation of endo-dicyclopentadiene with zinc carbenoids:Effects of solvent and(ICH2)2Zn[J].Journal of Organic Chemistry,2012,77(22):10065-10072.
[14]KONG J,ROY D,LENOIR D,et al.2-Norbornyl ion-pair leakage in electrophilic addition of HCl to nortricy-clene and norbornene[J].Organic Letter,2009,11(20):4684-4687.
[15]邹吉军,张香文,蒋强,等.由环戊二烯和桥式双环戊二烯催化合成液体喷气燃料的方法[P].中国专利:200710057328.7,2009-07-08.
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[17]张香文,姜凯,邹吉军,等.双环戊二烯加压连续聚合制备高能量密度燃料[J].化工学报,2007,58(10):2658-2663.ZHANG Xiangwen,JIANG Kai,ZOU Jijun,et al.Continuous oligomerization of dicyclopentadiene at elevated pressure for synthesis of high energy density fuel[J].2007,58(10):2658-2663.
[18]ZHANG X,JIANG Q,XIONG Z,et al.Diels-alder addition of dicyclopentadiene with cyclopentadiene in polar solvents[J].Chemical Research in Chinese Universities,2008,24(2):175-179.
[19]WANG L,ZHANG X,ZOU J,et al.Acid-catalyzed isomerization of tetrahydro tricyclopentadiene:Synthesis of high-energy-density liquid fuel[J].Energy Fuels,2009,23(5):2383-2388.
[20]LI Y,ZOU J,ZAHNG X,et al.Product distribution of tricyclopentadiene from cycloaddition of dicyclopenta-diene and cyclopentadiene:A theoretical and experimental study[J].Fuel,2010,89(9):2522-2527.
[21]OUTCALT S L,LAESECKE A.Measurements of density and speed of sound of JP-10 and a comparison to rocket propellants and jet fuels[J].Energy Fuels,2011,25(3):1132-1139.
[22]SULD G,SCHNEIDER A,MYERS H K.Dimerization of norbornadiene to exoexo hexacycclic dimmer[P].US Patent:4207080,1980-10-06.
[23]AUDEH C A,BOULTON J R,KREMER R A,et al.Catalytic norbornylation of aromatics[P].US Patent:5461180,1995-10-24.
[24]李辉,朴英,曹文杰,等.高热安定性煤基喷气燃料理化性能的试验研究[J].煤炭学报,2016,41(9):2347-2351.LI Hui,PIAO Ying,CAO Wenjie,et al.Experimental study on the physicochemical properties of advanced thermal stability coalbased jet fuel[J].Journal of China Coal Society,2016,41(9):2347-2351
[25]BUTNARK S,BADGER M W,SCHOBERT H H,et al.Coal-based jet fuel:Composition,thermal stability and properties[J].American Chemical Society,Division of Fuel Chemistry Preprints of Symposia,2004,48(1):158-161.
[26]李军芳,赵学社,李文博,等.煤直接液化油航空煤油馏分的性质与组分分析[J].煤炭转化,2013,36(4):29-31.LI Junfang,ZHAO Xueshe,LI Wenbo,et al.Property and constituents analysis of coal direct liquefied aviation kerosene distillate[J].Coal Conversion,2013,36(4):29-31.
[27]刘华,毛学锋,陈贵锋,等.烃类燃料及其制备方法[P].中国专利:201710440691.0,2017-06-12.
[28]王宇.催化重整加工煤直接液化石脑油工艺特点[J].化工时刊,2016,30(2):19-22.WANG Yu.The characteristics of catalytic reforming process of naphtha from direct coal liquefaction[J].Chemical Industry Times,2016,30(2):19-22.
[29]呼跃军.首次以煤为原料产出国标车用汽油煤基合成石脑油催化重整获突破[J].中国石油和化工,2014(6):48.HU Yuejun.Production of national standard vehicle gasoline for the first time with coal as raw material breakthrough in catalytic reforming of coal based naphtha[J].China’s Petroleum and Chemical Industry,2014(6):48.
[30]李海军.煤直接液化车用汽油制备研究[J].煤化工,2016,44(2):10-14.LI Haijun.Study on the vehicle gasoline preparation via direct coal liquefaction[J].Coal Chemical Industry,2016,44(2):10-14.
[31]黄珏.煤直接液化轻质油的芳烃分离与液化产物再加氢行为研究[D].上海:华东理工大学,2011.
[32]王秀红.煤液化油中芳烃/环烷烃分离规律及其机理研究[D].太原:太原理工大学,2011.
[33]田敬宇.煤液化油的芳烃分离及油煤浆温粘关系的研究[D].上海:华东理工大学,2014.
[34]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.
[2]熊中强,米镇涛,张香文,等.合成高密度烃类燃料研究进展[J].化学进展,2005,17(2):360-367.XIONG Zhongqiang,MI Zhentao,ZHANG Xiangwen,et al.Development of synthesized high-density hydrocarbon fuels[J].Progress in Chemistry,2005,17(2):360-367.
[3]欧育湘,刘进全.高能量密度化合物[M].北京:国防工业出版社,2005.
[4]张怀安,胡雁,朱成平,等.RP-3+100喷气燃料使用性能探讨[A].中国化学会第五届全国化学推进剂学术会议论文集[C].2011.
[5]马洪安.国产RP--3航空煤油着火与燃烧特性的实验与数值研究[D].大连:大连理工大学,2016.
[6]邹吉军,张香文,王莅,等.高密度液体碳氢燃料合成及应用进展[J].含能材料,2007,15(4):411-415.ZOU Jijun,ZHANG Xiangwen,WANG Li,et al.Process on the synthesis and application of high-density liquid hydrocarbon fuels[J].Chinese Journal of Energetic Materials,2007,15(4):411-415.
[7]DIELS Otto,ALDER Kurt.Synthesen in der hydroaromatischen Reihe[J].European Journal of Organic Chemistry,2010,460(1):98-122.
[8]刑其毅,裴伟伟,徐瑞秋,等.基础有机化学:下册(第4版)[M].北京:北京大学出版社,2017.
[9]徐文媛,杜瑞焕,龙威.Diels-Alder反应的理论研究新进展[J].华东交通大学学报,2011,28(3):60-64.XU Wenyuan,DU Ruihuan,LONG Wei.Progress of the theory study on diels-alder reactions[J].Journal of East China Jiaotong University,2011,28(3):60-64.
[10]CHUNG H S,CHEN C S H,KREMER R A,et al.Recent developments in high-energy density liquid hydrocarbon fuels[J].Energy Fuels,1999,13(3):641-649.
[11]STRIEBICH R C,LAWRENCE J.Thermal decomposition of highenergy density materials at high pressure and temperature[J].Journal of Analytical&Applied Pyrolysis,2003,70(2):339-352.
[12]KONG J,GALABOV B,KOLEVA G,et al.The inherent competition between addition and substitution reactions of Br2 with benzene and arenes[J].Angewandte Chemie International Edition,2011,50(30):6809-6813.
[13]FENG R,ZOU J,ZHANG X,et al.Theoretical study on cyclopropanation of endo-dicyclopentadiene with zinc carbenoids:Effects of solvent and(ICH2)2Zn[J].Journal of Organic Chemistry,2012,77(22):10065-10072.
[14]KONG J,ROY D,LENOIR D,et al.2-Norbornyl ion-pair leakage in electrophilic addition of HCl to nortricy-clene and norbornene[J].Organic Letter,2009,11(20):4684-4687.
[15]邹吉军,张香文,蒋强,等.由环戊二烯和桥式双环戊二烯催化合成液体喷气燃料的方法[P].中国专利:200710057328.7,2009-07-08.
[16]邹吉军,潘伦,李红娇,等.酸催化降冰片烯二聚制备高能燃料的方法[P].中国专利:200810153734.8,2011-04-27.
[17]张香文,姜凯,邹吉军,等.双环戊二烯加压连续聚合制备高能量密度燃料[J].化工学报,2007,58(10):2658-2663.ZHANG Xiangwen,JIANG Kai,ZOU Jijun,et al.Continuous oligomerization of dicyclopentadiene at elevated pressure for synthesis of high energy density fuel[J].2007,58(10):2658-2663.
[18]ZHANG X,JIANG Q,XIONG Z,et al.Diels-alder addition of dicyclopentadiene with cyclopentadiene in polar solvents[J].Chemical Research in Chinese Universities,2008,24(2):175-179.
[19]WANG L,ZHANG X,ZOU J,et al.Acid-catalyzed isomerization of tetrahydro tricyclopentadiene:Synthesis of high-energy-density liquid fuel[J].Energy Fuels,2009,23(5):2383-2388.
[20]LI Y,ZOU J,ZAHNG X,et al.Product distribution of tricyclopentadiene from cycloaddition of dicyclopenta-diene and cyclopentadiene:A theoretical and experimental study[J].Fuel,2010,89(9):2522-2527.
[21]OUTCALT S L,LAESECKE A.Measurements of density and speed of sound of JP-10 and a comparison to rocket propellants and jet fuels[J].Energy Fuels,2011,25(3):1132-1139.
[22]SULD G,SCHNEIDER A,MYERS H K.Dimerization of norbornadiene to exoexo hexacycclic dimmer[P].US Patent:4207080,1980-10-06.
[23]AUDEH C A,BOULTON J R,KREMER R A,et al.Catalytic norbornylation of aromatics[P].US Patent:5461180,1995-10-24.
[24]李辉,朴英,曹文杰,等.高热安定性煤基喷气燃料理化性能的试验研究[J].煤炭学报,2016,41(9):2347-2351.LI Hui,PIAO Ying,CAO Wenjie,et al.Experimental study on the physicochemical properties of advanced thermal stability coalbased jet fuel[J].Journal of China Coal Society,2016,41(9):2347-2351
[25]BUTNARK S,BADGER M W,SCHOBERT H H,et al.Coal-based jet fuel:Composition,thermal stability and properties[J].American Chemical Society,Division of Fuel Chemistry Preprints of Symposia,2004,48(1):158-161.
[26]李军芳,赵学社,李文博,等.煤直接液化油航空煤油馏分的性质与组分分析[J].煤炭转化,2013,36(4):29-31.LI Junfang,ZHAO Xueshe,LI Wenbo,et al.Property and constituents analysis of coal direct liquefied aviation kerosene distillate[J].Coal Conversion,2013,36(4):29-31.
[27]刘华,毛学锋,陈贵锋,等.烃类燃料及其制备方法[P].中国专利:201710440691.0,2017-06-12.
[28]王宇.催化重整加工煤直接液化石脑油工艺特点[J].化工时刊,2016,30(2):19-22.WANG Yu.The characteristics of catalytic reforming process of naphtha from direct coal liquefaction[J].Chemical Industry Times,2016,30(2):19-22.
[29]呼跃军.首次以煤为原料产出国标车用汽油煤基合成石脑油催化重整获突破[J].中国石油和化工,2014(6):48.HU Yuejun.Production of national standard vehicle gasoline for the first time with coal as raw material breakthrough in catalytic reforming of coal based naphtha[J].China’s Petroleum and Chemical Industry,2014(6):48.
[30]李海军.煤直接液化车用汽油制备研究[J].煤化工,2016,44(2):10-14.LI Haijun.Study on the vehicle gasoline preparation via direct coal liquefaction[J].Coal Chemical Industry,2016,44(2):10-14.
[31]黄珏.煤直接液化轻质油的芳烃分离与液化产物再加氢行为研究[D].上海:华东理工大学,2011.
[32]王秀红.煤液化油中芳烃/环烷烃分离规律及其机理研究[D].太原:太原理工大学,2011.
[33]田敬宇.煤液化油的芳烃分离及油煤浆温粘关系的研究[D].上海:华东理工大学,2014.
[34]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.