二苯乙烯对秸秆纤维素超临界乙醇裂解转化液化产物的影响
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摘要
以1,1-二苯乙烯(DPE)为阻聚剂,采用高压反应釜对玉米秸秆纤维素进行超临界乙醇液化,探究DPE浓度(用量)和反应温度对纤维素裂解碎片转化成液化产物的影响。结果表明,DPE浓度增加,挥发分收率降低了25.4%,生物油收率增加了19.9%,收率最高达39.8%,纤维素转化率有所下降;反应温度升高,纤维素转化率迅速增加到85.5%,挥发分也急剧升高,生物油收率最高为34.6%。GC-MS结果显示,生物油主要包括酮类、酯类、烃类等平台化合物以及较多的联苯化合物。DPE浓度过高,结合大量的纤维素裂解片段(乙基、羟基、甲基、氢等)形成联苯类化合物产生较强的空间位阻效应,使得纤维素裂解及活性片段转化成平台化合物的反应受到抑制,两者之间是一个竞争过程;温度升高,乙醇自由基活性增强,其对纤维素裂解的促进作用逐渐超过DPE对纤维素裂解的抑制作用,平台化合物收率有所升高。
With 1,1-diphenylethene(DPE) as the polymerization inhibitor,the effects of DPE concentration(dosage) and reaction temperature on the active fragments transforming to liquefaction products during cellulose liquefaction in supercritical ethanol were investigated using an autoclave.As the DPE concentration increases,the yield of volatile compounds decreases by 25.4%,while the yield of bio-oil increases to 39.8%,and the cellulose conversion rate decreases gradually.With the increasing of reaction temperature,the cellulose conversion rate reaches to 85.5% sharply and the volatile compounds also increases fastly,but the maximum bio-oil yield drops to 34.6%.GC-MS analysis shows that ketones,esters,alkanes,alcohols,acids and the DPE derivatives are dominant platform chemicals in the bio-oil.A lot of active fragments(such as CH_3CH_2-,HO-,H-,CH_3-,etc.)produced from cellulose pyrolysis in supercritical ethanol are trapped by a higher concentration of DPE to form DPE derivatives,which has a strong steric effect on the fragments transforming to platform chemicals.With the increasing of temperature,the enhanced pyrolysis of cellulose by ethanol radicals is more significant in comparison with the inhibition of DPE,resulting in an improvement in the content of platform chemicals.
With 1,1-diphenylethene(DPE) as the polymerization inhibitor,the effects of DPE concentration(dosage) and reaction temperature on the active fragments transforming to liquefaction products during cellulose liquefaction in supercritical ethanol were investigated using an autoclave.As the DPE concentration increases,the yield of volatile compounds decreases by 25.4%,while the yield of bio-oil increases to 39.8%,and the cellulose conversion rate decreases gradually.With the increasing of reaction temperature,the cellulose conversion rate reaches to 85.5% sharply and the volatile compounds also increases fastly,but the maximum bio-oil yield drops to 34.6%.GC-MS analysis shows that ketones,esters,alkanes,alcohols,acids and the DPE derivatives are dominant platform chemicals in the bio-oil.A lot of active fragments(such as CH_3CH_2-,HO-,H-,CH_3-,etc.)produced from cellulose pyrolysis in supercritical ethanol are trapped by a higher concentration of DPE to form DPE derivatives,which has a strong steric effect on the fragments transforming to platform chemicals.With the increasing of temperature,the enhanced pyrolysis of cellulose by ethanol radicals is more significant in comparison with the inhibition of DPE,resulting in an improvement in the content of platform chemicals.
引文
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[11]黎巍,解新安,汤成正,李雁,李璐,王娅莉,魏星,樊荻.亚/超临界乙醇中羟基和氢自由基作用下的纤维素液化行为[J].燃料化学学报,2016,44(4):415-421.(LI Wei,XIE Xin-an,TAN Cheng-zheng,LI Yan,LI Lu,WANG Ya-li,WEI Xing,FAN Di.Effects of hydroxyl and hydrogen free radicals on the liquefaction of cellulose in sub/supercritical ethanol[J].J Fuel Chem Technol,2016,44(4):415-421.)
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[14]GUO Z,BAI Z,BAI J,WANG Z,LI W.Co-liquefaction of lignite and sawdust under syngas[J].Fuel Process Technol,2011,92(1):119-125.
[15]OGIHARA Y,JR R L S,INOMATA H,ARAI K.Direct observation of cellulose dissolution in subcritical and supercritical water over a wide range of water densities(550-1 000 kg/m3)[J].Cellulose,2005,12(6):595-606.
[16]陶红秀,解新安,汤成正,田文广.玉米秸秆纤维素在亚/超临界乙醇中液化生成酮类化合物的机理探讨[J].燃料化学学报,2013,41(1):60-66.(TAO Hong-xiu,XIE Xin-an,TANG Cheng-zheng,TIAN Wen-guang.Mechanism of ketones formation from cellulose liquefaction in suband supercritical ethanol[J].J Fuel Chem Technol,2013,41(1):60-66.)
[17]郭贵全,王红娟,谌凡更.植物纤维在供氢溶剂中的液化反应[J].纤维素科学与技术,2003,11(2):41-50.(GUO Gui-quan,WANG Hong-juan,CHEN Fan geng.Thermochemical liquefaction of lignocellulosic materious in hydrogen-donor solvent[J].J Cellulose Sci Technol,2003,11(2):41-50.)
[18]MORTENSEN P M,GRUNWALDT J,JENSEN P A,KNUDSEN K G,JENSEN A D.A review of catalytic upgrading of bio-oil to engine fuels[J].Appl Catal A:Gen,2011,407(1/2):1-19.
[19]TANG C,TAO H,ZHAN X,XIE X.Mechanism of esters formation during cellulose liquefaction in sub-and supercritical ethanol[J].Bioresour,2014,9(3):4946-4957.
[20]包桂蓉.纤维素在高温高压溶剂中的降解研究[D].昆明理工大学,2010.(BAO Gui-rong.Study on cellulose degradation in high temperature and high pressure solvents[D].Kunming:Kunming University of Science and Technology,2010.)
[21]廖航涛.果糖与纤维二糖快速热解机理研究[D].华北电力大学,2014.(LIAO Hang-tao.Mechanism of fast pyrolysis of fructose and cellubiose[D].Beijing:North China Electric Power University,2014.)
[22]耿中峰.纤维素热裂解机理的理论和实验研究[D].天津大学,2010.(GENG Zhong-feng.Theoretical and experimental study on mechanism of cellulose pyrolysis[D].Tianjin:Tianjin University,2010.)
[23]黄金保.纤维素快速热解机理的分子模拟研究[D].重庆大学,2010.(HUANG Jin-bao.Molecular simulation sdudy of pyrolysis mechanism of cellulose[D].Chongqing:Chongqing University,2010.)
[24]石宁,刘琪英,王铁军,张琦,廖玉河,马隆龙,蔡炽柳.一步催化转化纤维素制备化学品的研究进展[J].新能源进展,2014(4):245-253.(SHI Ning,LIU Qi-ying,WANG Tie-jun,ZHANG Qi,LIAO Yu-he,MA Long-long,CAI Chi-liu.Progress in one-pot catalytic transformation of cellulose into valuable chemicals[J].Advan New Renew Energy,2014(4):245-253.)
[25]LI W,XIE X,TANG C,LI Y,LI L,WANG Y,FAN D,WEI X.The distribution of bio-oil components with the effects of sub/supercritical ethanol and free radicals during cellulose liquefaction[J].Bioresour,2016,11(4):9771-9788.
[26]黄金保,刘朝,魏顺安,黄晓露,李豪杰.纤维素热解形成左旋葡聚糖机理的理论研究[J].燃料化学学报,2011(8):590-594.(HUANG Jin-bao,LIU Chao,WEI Shun-an.A theoretical study on the mechanism of levoglucosan formation in cellulose pyrolysis[J].J Fuel Chem Technol,2011(8):590-594.)
[27]黄金保,刘朝,魏顺安.纤维素单体热解机理的热力学研究[J].化学学报,2009,67(18):2081-2086.(HUANG Jin-bao,LIU Chao,WEI Shun-an.Thermodynamic studies of pyrolysis mechanism of cellulose monomer[J].Asta Chimica Sinica,2009,67(18):2081-2086.)
[2]HASSANZADEH S,AMINLASHGARI N,HAKKARAINEN M.Chemo-selective high yield microwave assisted reaction turns cellulose to green chemicals[J].Carbohydr Polym,2014,112:448-457.
[3]YAMAZAKI J,MINAMI E,SAKA S.Liquefaction of beech wood in various supercritical alcohols[J].J Wood Sci,2006,52(6):527-532.
[4]MAZAHERI H,LEE K T,BHATIA S,MOHAMED A R.Sub/supercritical liquefaction of oil palm fruit press fiber for the production of biooil:Effect of solvents[J].Bioresour Technol,2010,101(19):7641-7647.
[5]郑朝阳,解新安,陶红秀,郑璐丝,李雁.亚/超临界乙醇液化秸秆纤维素解聚反应研究与机理初探[J].燃料化学学报,2012(5):526-532.(ZHENG Chao-yang,XIE Xin-an,TAO Hong-xiu,ZHENG Lu-si,LI Yan.Depolymerization of stalk cellulose during its liquefaction in suband supercritical ethanol[J].J Fuel Chem Technol,2012(5):526-532.)
[6]陶红秀,解新安,郑朝阳,汤成正,战晓青.玉米秸秆纤维素在亚/超临界乙醇中的液化行为研究[J].西北农林科技大学学报(自然科学版),2014,42(1):196-204.(TAO Hong-xiu,XIE Xin-an,ZHENG Chao-yang,ZHAN Xiao-qing.Liquefaction of cornstalk cellulose in sub/super-critical ethanol[J].J Northwest Univ Agri For(Nat Sci Ed),2014,42(1):196-204.)
[7]陈晓菲.稻秆粉末醇解产物的分析和醇解机理研究[D].武汉:武汉科技大学,2008.(CHEN Xiao-fei.Analysis of the products from alkanolysis of the rice-stalk powder and related mechanism study[D].Wuhan:Wuhan University of Science and Technology,2008.)
[8]MURNIEKS R,KAMPARS V,MALINS K,APSENIECE L.Hydrotreating of wheat straw in toluene and ethanol[J].Bioresour Technol,2014,163:106-111.
[9]唐仕荣,路瑶,周磊,夏纯杰,魏贤勇,宗志敏.玉米秆超临界乙醇解聚产物分析[J].安徽农业科学,2009,37(11):4869-4870.(TANG Shi-rong.Analysis of depolymerization product of cornstalk in supercritical ethanol[J].J Anhui Agri Sci,2009,37(11):4869-4870.)
[10]ZHENG C,TAO H,XIE X.Distribution and characterizations of liquefaction of celluloses in sub-and super-critical ethanol[J].Bioresour,2013,8(1):648-662.
[11]黎巍,解新安,汤成正,李雁,李璐,王娅莉,魏星,樊荻.亚/超临界乙醇中羟基和氢自由基作用下的纤维素液化行为[J].燃料化学学报,2016,44(4):415-421.(LI Wei,XIE Xin-an,TAN Cheng-zheng,LI Yan,LI Lu,WANG Ya-li,WEI Xing,FAN Di.Effects of hydroxyl and hydrogen free radicals on the liquefaction of cellulose in sub/supercritical ethanol[J].J Fuel Chem Technol,2016,44(4):415-421.)
[12]赵敏坚,石艳,付志峰.1,1-二苯基乙烯存在下丙烯酸丁酯的聚合机理研究[J].北京化工大学学报(自然科学版),2014(3):64-68.(ZHAO Min-jian,SHI Yan,FU Zhi-feng.Polymerization mechanism of n-butyl acrylate in the presence of 1,1-diphenylethylene[J].J Bejing Univ Chem Technol(Nat Sci),2014(3):64-68.
[13]马金红,赵敏坚,石艳,付志峰.1,1-二苯基乙烯存在下甲基丙烯酸甲酯的自由基聚合研究[J].北京化工大学学报(自然科学版),2011(4):79-83.(MA Jin-hong,ZHAO Min-jian,SHI Yan,FU Zhi-feng.Radical polymerization of methyl methacrylate in the presence of 1,1-diphenylethylene[J].J Bejing Univ Chem Technol(Nat Sci),2011(4):79-83.)
[14]GUO Z,BAI Z,BAI J,WANG Z,LI W.Co-liquefaction of lignite and sawdust under syngas[J].Fuel Process Technol,2011,92(1):119-125.
[15]OGIHARA Y,JR R L S,INOMATA H,ARAI K.Direct observation of cellulose dissolution in subcritical and supercritical water over a wide range of water densities(550-1 000 kg/m3)[J].Cellulose,2005,12(6):595-606.
[16]陶红秀,解新安,汤成正,田文广.玉米秸秆纤维素在亚/超临界乙醇中液化生成酮类化合物的机理探讨[J].燃料化学学报,2013,41(1):60-66.(TAO Hong-xiu,XIE Xin-an,TANG Cheng-zheng,TIAN Wen-guang.Mechanism of ketones formation from cellulose liquefaction in suband supercritical ethanol[J].J Fuel Chem Technol,2013,41(1):60-66.)
[17]郭贵全,王红娟,谌凡更.植物纤维在供氢溶剂中的液化反应[J].纤维素科学与技术,2003,11(2):41-50.(GUO Gui-quan,WANG Hong-juan,CHEN Fan geng.Thermochemical liquefaction of lignocellulosic materious in hydrogen-donor solvent[J].J Cellulose Sci Technol,2003,11(2):41-50.)
[18]MORTENSEN P M,GRUNWALDT J,JENSEN P A,KNUDSEN K G,JENSEN A D.A review of catalytic upgrading of bio-oil to engine fuels[J].Appl Catal A:Gen,2011,407(1/2):1-19.
[19]TANG C,TAO H,ZHAN X,XIE X.Mechanism of esters formation during cellulose liquefaction in sub-and supercritical ethanol[J].Bioresour,2014,9(3):4946-4957.
[20]包桂蓉.纤维素在高温高压溶剂中的降解研究[D].昆明理工大学,2010.(BAO Gui-rong.Study on cellulose degradation in high temperature and high pressure solvents[D].Kunming:Kunming University of Science and Technology,2010.)
[21]廖航涛.果糖与纤维二糖快速热解机理研究[D].华北电力大学,2014.(LIAO Hang-tao.Mechanism of fast pyrolysis of fructose and cellubiose[D].Beijing:North China Electric Power University,2014.)
[22]耿中峰.纤维素热裂解机理的理论和实验研究[D].天津大学,2010.(GENG Zhong-feng.Theoretical and experimental study on mechanism of cellulose pyrolysis[D].Tianjin:Tianjin University,2010.)
[23]黄金保.纤维素快速热解机理的分子模拟研究[D].重庆大学,2010.(HUANG Jin-bao.Molecular simulation sdudy of pyrolysis mechanism of cellulose[D].Chongqing:Chongqing University,2010.)
[24]石宁,刘琪英,王铁军,张琦,廖玉河,马隆龙,蔡炽柳.一步催化转化纤维素制备化学品的研究进展[J].新能源进展,2014(4):245-253.(SHI Ning,LIU Qi-ying,WANG Tie-jun,ZHANG Qi,LIAO Yu-he,MA Long-long,CAI Chi-liu.Progress in one-pot catalytic transformation of cellulose into valuable chemicals[J].Advan New Renew Energy,2014(4):245-253.)
[25]LI W,XIE X,TANG C,LI Y,LI L,WANG Y,FAN D,WEI X.The distribution of bio-oil components with the effects of sub/supercritical ethanol and free radicals during cellulose liquefaction[J].Bioresour,2016,11(4):9771-9788.
[26]黄金保,刘朝,魏顺安,黄晓露,李豪杰.纤维素热解形成左旋葡聚糖机理的理论研究[J].燃料化学学报,2011(8):590-594.(HUANG Jin-bao,LIU Chao,WEI Shun-an.A theoretical study on the mechanism of levoglucosan formation in cellulose pyrolysis[J].J Fuel Chem Technol,2011(8):590-594.)
[27]黄金保,刘朝,魏顺安.纤维素单体热解机理的热力学研究[J].化学学报,2009,67(18):2081-2086.(HUANG Jin-bao,LIU Chao,WEI Shun-an.Thermodynamic studies of pyrolysis mechanism of cellulose monomer[J].Asta Chimica Sinica,2009,67(18):2081-2086.)