OALib Journal期刊
ISSN: 2333-9721
费用:99美元
|
|
|
吡喃木糖和o-乙酰基吡喃木糖热解形成羟基乙醛的机理研究
, PP. 185-194
Keywords: 吡喃木糖,o-乙酰基,热解,羟基乙醛,密度泛函理论
Abstract:
?以半纤维素主要成分木聚糖的两种单体——吡喃木糖和o-乙酰基吡喃木糖为模型化合物,运用密度泛函理论(dft),采用b3lyp方法和6-31+g(d,p)基组进行计算,研究了吡喃木糖热解形成haa的6条可能的反应路径和o-乙酰基吡喃木糖热解形成haa的3条可能的反应路径。由此确定了吡喃木糖热解形成haa的最优路径为:吡喃木糖首先开环得到链式木糖,然后c3羟基和c2氢脱水,随后经重排和逆醇醛缩合反应生成包含c4/c5的haa;该路径的决速步骤为脱水反应,能垒为253.3kj/mol。o-乙酰基吡喃木糖热解形成haa的最优路径为:o-乙酰基吡喃木糖首先支链断裂脱出乙酸(aa),开环后的链式中间体经氢转移反应得到包含c4/c5的haa;该路径的决速步骤为最后的氢转移反应,能垒为317.6kj/mol。
References
[1] | bridgwaterav,peacockegvc.fastpyrolysisprocessesforbiomass[j].renewsustenergyrev,2000,4(1):1-73.
|
[2] | wangs,liangt,rub,guox.mechanismofxylanpyrolysisbypy-gc/ms[j].chemreschinuniv,2013,29(4):782-787.
|
[3] | pondergr,richardsgn.thesynthesisandpyrolysisofaxylan[j].carbohydrres,1991,211(1):143-145.
|
[4] | 黄金保,刘朝,童红,李伟民,伍丹.o-乙酰基-吡喃木糖热解反应机理的理论研究[j].燃料化学学报,2013,41(3):285-293.(huangjin-bao,liuchao,tonghong,liwei-min,wudan.theoreticalstudiesonpyrolysismechanismofo-acetyl-xylopyranose[j].jfuelchemtechnol,2013,41(3):285-293.)
|
[5] | mohand,pittmancu,steeleph.pyrolysisofwood/biomassforbio-oil:acriticalreview[j].energyfuel,2006,20(3):848-889.
|
[6] | venderboschrh,prinsw.fastpyrolysistechnologydevelopment[j].biofuelsbioprodbioref,2010,4(2):178-208.
|
[7] | 刘利军,蒋剑春,黄海涛.木聚糖cp-gc-ms法裂解行为研究[j].林业化学与工业,2010,30(1):1-6.(liuli-jun,jiangjian-chun,huanghai-tao.studyoncurie-pointpyrolysisofxlanundercp-gc-msconditions[j].chemindforprod,2010,30(1):1-6.)
|
[8] | shendk,gus,bridgwaterav.studyonthepyrolyticbehaviourofxylan-basedhemicelluloseusingtg-ftirandpy-gc-ftir[j].janalapplpyrolysis,2010,87(2):199-206.
|
[9] | piskorzj,radleind,scootds.onthemechanismoftherapidpyrolysisofcellulose[j].janalapplpyrolysis,1986,9(2):121-137.
|
[10] | 陆强,廖航涛,张阳,张俊姣,董长青.果糖低温快速热解制备5-羟甲基糠醛的机理研究[j].燃料化学学报,2013,41(9):1071-1076.(luqiang,liaohang-tao,zhangyang,zhangjun-jiao,dongchang-qing.reactionmechanismoflow-temperaturefastpyrolysisoffructosetoproduce5-hydroxymethylfurfural[j].jfuelchemtechnol,2013,41(9):1071-1076.)
|
[11] | zhangx,yangw,dongc.levoglucosanformationmechanismsduringcellulosepyrolysis[j].janalapplpyrolysis,2013,104:19-27.
|
[12] | 黄金保,刘朝,任丽荣,童红,李伟民,伍丹.木质素模化物紫丁香酚热解机理的量子化学研究[j].燃料化学学报,2013,41(6):657-666.(huangjin-bao,liuchao,renli-rong,tonghong,liwei-min,wudan.studiesonpyrolysismechanismofsyringolasligninmodelcompoundbyquantumchemistry[j].jfuelchemtechnol,2013,41(6):657-666.)
|
[13] | 张智,刘朝,李豪杰,黄金宝,黄晓露.木聚糖单体热解机理的理论研究[j].化学学报,2011,69(18):2099-2107.(zhangzhi,liuchao,lihao-jie,huangjin-bao,huangxiao-lu.theoreticalstudiesofpyrolysismechainsmofxylanmonomer[j].jchinchemsoc,2011,69(18):2099-2107.)
|
[14] | huangj,liuc,tongh,liw,wud.theoreticalstudiesonpyrolysismechanismofxylopyranose[j].computtheorchem,2012,1001:44-50.
|
[15] | zhangx,lij,yangw,blasiakw.formationmechanismoflevoglucosanandformaldehydeduringcellulosepyrolysis[j].energyfuels,2011,25(8):3739-3746.
|
[16] | wangs,guox,liangt,zhouy,luoz.mechanismresearchoncellulosepyrolysisbypy-gc/msandsubsequentdensityfunctionaltheorystudies[j].bioresourtechnol,2012,104:722-728.
|
[17] | parthasarathir,romerora,redondoa,gnanakarans.theoreticalstudyoftheremarkablydiverselinkagesinlignin[j].chemphyslett,2011,2(20):2660-2666.
|
[18] | kims,chmelysc,nimlosmr,bombleyj,fousttd,patonrs,beckhamgt.computationalstudyofbonddissociationenthalpiesforalargerangeofnativeandmodifiedlignins[j].chemphyslett,2011,2(22):2846-2852.
|
[19] | wangs,rub,linh,luoz.degradationmechanismofmonosaccharidesandxylanunderpyrolyticconditionswiththeoreticmodelingontheenergyprofiles[j].bioresourtechnol,2013,143:378-383.
|
[20] | beckead.density-functionalthermochemistry.iii.theroleofexactexchange[j].jchemphys,1993,98(7):5648-5652.
|
[21] | miehlichb,savina,stollh,preussh.resultsobtainedwiththecorrelationenergydensityfunctionalsofbeckeandlee,yangandparr[j].chemphyslett,1989,157(3):200-206.
|
[22] | lynchbj,truhlardg.howwellcanhybriddensityfunctionalmethodspredicttransitionstategeometriesandbarrierheights[j].jphyschema,2001,105(13):2936-2941.
|
[23] | zhangx,yangw,blasiakw.thermaldecompositionmechanismoflevoglucosanduringcellulosepyrolysis[j].janalapplpyrolysis,2012,96:110-119.
|
[24] | zhangx,yangw,blasiakw.kineticsstudyonthermaldissociationoflevoglucosanduringcellulosepyrolysis[j].fuel,2013,109:476-483.
|
[25] | wongmw.vibrationalfrequencypredictionusingdensityfunctionaltheory[j].chemphyslett,1996,256(4/5):391-399.
|
[26] | gonzalezc,schlegelhb.animprovedalgorithmforreactionpathfollowing[j].jchemphys,1989,90(4):2154-2161.
|
[27] | frischmj,trucksgw,schlegelhb,etal.gaussian03,pittsburghpa:guassian,inc,2003.
|
[28] | nimlosmr,blanksbysj,ellisongb,evansrj.enhancementof1,2-dehydrationofalcoholsbyalkalicationsandprotons:amodelfordehydrationofcarbohydrates[j].janalapplpyrolysis,2003,66(1/2):3-27.
|
Full-Text
|
|
Contact Us
service@oalib.com QQ:3279437679 
WhatsApp +8615387084133
|
|