1、null11 null null l : 2007- 09- 27 “: 8p V S4 “(20060311)bTe:f (1973- ), 3, g ,v,CV Y/ Tb =JZE张启同1,于永波1,赵宁2,郭启文1,张铸伟1,欧阳建锋1,柴继勇1(1. K , gnull 271601;2.S S , null 030001)K1: =J # -,W%8 X| =JZE #/ Zb1oM: =J;E;E; U ?Ems |: TQ225. 52null null null null nullDS M :Anull null null nullcI|: 1008-021X(2007)11
2、-0015- 03Research Progress on the Synthesis ofDimethyl CarbonateZHANG Q i- tong1, YU Yong- bo1, ZHAO N ing2,GUO Qi-w en1, ZHANG Zhu-wei1, OUYONG Jian- feng1, CHAI Ji- yong1(1. ShandongAcidChemicalsCo.,Ltd., Feicheng271601,China;2. ShanxiInstituteofCoalChemistry, ChineseAcademy ofSciences, Taiyuan030
3、001, China)Abstract: Thephysico- chemicalproperties and the application prospectofdimethylcarbonate(DMC)were introduced. Theprogressof the research anddevelopmentof thecatalyst and theprocess forDMCsynthesiswerealso summarized.Key words: dimethylcarbonate(DMC); carboxylation; transesterification;met
4、hanolysis ofurea1null =J =J(DimethylCarbonate)eDMC, M sS =W1 s , H B i a aCA8,4null ,m90. 1null , 1. 069g/cm3, 4 , V?a a+ 4 bDMC, 1992 MDMC xYV d (Nontoxicsubstance):, 1b s0cCH3 -aCH3O-aCH3O-CO-a- CO-2 ?v,y7 zQ, V?apaara ? 3JaaJQ,? | J k4 k4; 7,$ F2, b 3 s H1 p,+Y Z A U F -;N,DMC zM , ,9$W 4 3a F44a
5、 0A5 5b2null =JZEZ“ - 3 - =JZE1:; EaJ?EaE U ?E ,/sY +ZE aZai sN b2. 1null; E; Eg; J?E, K* 3DMCo6,ZE; J?(J? ) , n5 3 oJ J, oJ JBQ 3 =J, ! K, c o , P , O ; ,yN b; 3V SPPG SBASF b2. 2nullJ?EZEJ?aBDMC,NE W -, Ob 31 p,y7 WS1, “- =J1ZEb2. 2. 1nullJ?AMEnull15nullf ,: =JZEnullnullnulliv EniChem 1983 M n5 AM
6、EDMC7,i1988 M LC 3, BHd; E =JL,$ =J bZE o ob4i/5Q,#AMEbQs ,Q T /:2CH3OH+ 1/2O2 +2CuClnull 2Cu(OCH3)Cl+H2OCO+ 2Cu(OCH3 )Clnull (CH3O)2CO+2CuCl2. 2. 2nullJ? MEUbe AME$ ,1992 M LC ME =Jb - ME:b E MEb2. 2. 2. 1nullb EZEQ :b TW,YV Mb Q V =J, Q9s :2NO+ 2CH3OH+ 1/2O2= 2CH3ONO+H2O2CH3ONO+CO= (CH3O)2CO+ 2NOE
7、A+ MQbBQ , Obv Q b= 1o,Qb JCOb4i/,? 3Q 3 =J,i 3NO 8bJ?Q 3 #BQ,7DMC5=Q 3,E J?- -DMCW m7 4s b2. 2. 2. 2nullEE AMEM,b4Fs CuC,l %CuClb4, %AME K5, OL s lb| MJ?COaO2 8YVb4%5Q , M3 =J:2CH3OH+ CO+ 1/2O2= (CH3O)2CO+H2OME /: 1)AME1,%5Q ,1s 3b4 , !gb2) Pb JDMC,Q Hq/,b4 p 9Fb3) F b J 3 Q, F , CO2 7 Od r PIBb2.
8、3nullE= E W E M , STexaco 4WE =JZE8 10bZEE,Qs vs,FQQ,Q T /:J?EM1,E(4CO2J?WE) l qa KlaQHqaVb “-S 3 , S = R 3ZEbV YdN sK, 6rm s.Yb2. 4null U J? =J U ?EU ?E v7 U J?TQ ,N ,V7 3, VR U ,Nd a 3 U +Y ? b/ |v U ,4 Fbg K B?Z 2005 M 5000t/a =J “bU ?E Vs L:W U ?E U ?Eb2. 4. 1nullW U ?EZE n5 U =?(1Y=?d=?)Q Q( Yd
9、), QJ? =Jb1Q T /:NH2CONH2+RnullCHOHRnullCHOHRnullCHORnullCHOCO +2NH3null16null SHANDONG CHEMICAL INDUSTRYnull null null null null null null null null null null null 2007 M36 null11 2CH3OH+RnullCHORnullCHOCORnullCHOHRnullCHOH+ COCH3OCH3ORnull,Rnull _0c1- 4V Q T V A,=?( Y=?d=?)Vh, U T,yN,Q U J?,K DMC
10、bZE U q Y4 X,7 Os 9iv5; + 8 Doya11, 12sY x S S M1 b2. 4. 2null U ?EMW U ?E, U J?DMC U ?EbQ T /bnull nullQ+ U n5J?d J J(MC), J JJ?B =J,i db , VT U b9 A, aQHqb4T/,VQ NCO2J?,K B =Jb 6,W J 9 Bo% , V/“4a j0 - z8bS S !9BQ/ , P QV$MQ8“,r Qs B8 “,B4 U q =J4, ACEE 13, 14b2. 5null =J ZE“ ZE,D9C =JZE, J?CO2 =J
11、Ea=J EaE#J JEb3null =J B1 s , - b 31 p# V?Z t 1 p, HY ?,yN,21 W =J|y -, / A| sS = W jb参考文献 1 Tundo P, Perosa A. Green organic synthesis: organiccarbonates as methylating agents J. Chem Record,2002, 2: 13 23.2 TundoP, SelvaM.ThechemistryofdimethylcarbonateJ.AccountsChem Res, 2002, 35(9): 706 716.3Z ,
12、o, 7. =J 4 4p J.p , 2000, (1): 26 28.4 d , Cl, ,o. =JT F4 N J. F, 1997, 13(3): 40 44.5 Joho F, Novak P. SNIFTIRS investigation of the oxidativedecomposition of organic- carbonate- based electrolytesfor lithium - ion cells J. ElectrochimicaActa, 2000,45: 3589 3599.6,y !,f). =J 3/ 8 J.% F, 1998, (6):
13、45 49.7 RomanoU, TeseiR,MauriM M, eta.l Synthesisofdimethylcarbonate from methano,l carbon monoxide, and oxgencatalyzed by copper compounds J. Ind Eng Chem ProdResRev, 1980, 19: 396 403.8 US, 4661609P. 1987.9 US, 4691041P. 1986.10 Knifton J F, Duranleau R G. Ethylene glycol- dimethylcarbonatecogenation J. JMolCata,l 1991, 67: 389.11 Doya, et a.l Process for the production of dialkylcarbonate: EP, 0638541A1P. 1994.12 Doya, et a.l Process for the production of dialkylcarbonate:US, 5489702P. 1996.13 h,l , ,. CN, 00120873XP.14 h,l . CN, 01108814. 1P.null17nullf ,: =JZE
