Zn-La复合氧化物催化剂用于甲醇与碳酸乙烯酯酯交换反应的研究（英文）
|
摘要
ZnO、La_2O_3和Zn-La复合氧化物催化剂用于甲醇与碳酸乙烯酯反应制备碳酸二甲酯和乙二醇。催化剂采用共沉淀法进行制备,并用BET、XRD、TG-DSC、CO_2-TPD和Hammett滴定等对催化剂进行表征。考察了Zn-La物质的量比、焙烧温度,反应条件(反应温度、反应时间、催化剂用量等)对催化剂活性的影响。结果表明,ZnLa复合氧化物物质的量比为2∶1,焙烧温度为500℃时,催化剂表现了较好的催化效果。催化剂的活性与催化剂表面的碱性强度和碱量有关,碱量越多催化剂的活性越好。
The transesterification of ethylene carbonate( EC) with methanol to synthesis dimethyl carbonate( DMC) and ethylene glycol( EG) over ZnO,La_2O_3 and Zn-La mixed oxides were explored. The catalysts were prepared by co-precipitation method and characterized by BET,XRD,TG-DSC,CO_2-TPD and Hammett titration. The influence of Zn/La atomic ratio,calcination temperature and reaction parameters( reaction temperature, reaction time, catalyst amount) on the catalytic activity were investigated. The results indicated that the binary Zn-La mixed oxide with Zn/La atomic ratio of 2 ∶1 calcined at 500 ℃ showed the highest catalytic performance for the title reaction due to its strongest basicity,and the amount of strong basic sites of the catalyst should be responsible for the high transesterification activity.
The transesterification of ethylene carbonate( EC) with methanol to synthesis dimethyl carbonate( DMC) and ethylene glycol( EG) over ZnO,La_2O_3 and Zn-La mixed oxides were explored. The catalysts were prepared by co-precipitation method and characterized by BET,XRD,TG-DSC,CO_2-TPD and Hammett titration. The influence of Zn/La atomic ratio,calcination temperature and reaction parameters( reaction temperature, reaction time, catalyst amount) on the catalytic activity were investigated. The results indicated that the binary Zn-La mixed oxide with Zn/La atomic ratio of 2 ∶1 calcined at 500 ℃ showed the highest catalytic performance for the title reaction due to its strongest basicity,and the amount of strong basic sites of the catalyst should be responsible for the high transesterification activity.
引文
[1]XU W,JI S,QUAN W,YU J.One-pot synthesis of dimethyl carbonate over basic zeolite catalysts[J].Mod Res Catal,2013,2:22-27.
[2]TAN H Z,WANG Z Q,XU Z N SUN J,XU Y P,CHEN Q S,CHEN Y M,GUO G C.Review on the synthesis of dimethyl carbonate[J].Catal Today,2018,https://doi.org/10.1016/j.cattod.2018.02.021.
[3]WU X,KANG M,YIN Y,WANG F,ZHAO N,XIAO F,WEI W,SUN Y.Synthesis of dimethyl carbonate by urea alcoholysis over Zn/Al bi-functional catalysts[J].Appl Catal A:Gen,2014,473:13-20.
[4]FILIPPIS P D,SCARSELLA M,BORGIANNI C,POCHETTI F.Production of dimethyl carbonate via alkylene carbonate transesterification catalyzed by basic salts[J].Energy Fuels,2006,20(1):17-20.
[5]ETA V,MAKI-ARVELA P,SALMINEN E,SALMI T,MURZIN D Y,MIKKOLA J P.The effect of alkoxide ionic liquids on the synthesis of dimethyl carbonate from CO2and methanol over Zr O2-M g O[J].Catal Lett,2011,141:1254-1261.
[6]REN M,REN J,HAO P,YANG J,WANG D,PEI Y,LIN J,LI Z.Influence of microwave irradiation on the structural properties of carbonsupported hollow copper nanoparticles and their effect on the synthesis of dimethyl carbonate[J].Chem Cat Chem,2016,8(4):861-871.
[7]SAADA R,ABOELAZAYEM O,KELLICI S,HEIL T,MORGAN D,LAMPRONTI G I,SAHA B.Greener synthesis of dimethyl carbonate using a novel tin-zirconia/graphene nanocomposite catalyst[J].Appl Catal B:Environ,2018,226:451-462.
[8]SANKAR M,SATAV S,MANIKANDAN P.Transesterification of cyclic carbonates to dimethyl carbonate using solid oxide catalyst at ambient conditions:Environmentally benign synthesis[J].Chem Sus Chem,2010,3(5):575-578.
[9]TAMBOLI A H,CHAUGULE A A,KIM H.Catalytic developments in the direct dimethyl carbonate synthesis from carbon dioxide and methanol[J].Chem Eng J,2017,323:530-544.
[10]JAGTAP S R,BHOR M D,BHANAGE B M.Synthesis of dimethyl carbonate via transesterification of ethylene carbonate with methanol using poly-4-vinyl pyridine as a novel base catalyst[J].Catal Commun,2008,9(9):1928-1931.
[11]ABIMANYU H,KIM C S,AHN B S,YOO K S.Synthesis of dimethyl carbonate by transesterification with various Mg O-Ce O2mixed oxide catalysts[J].Catal Lett,2007,118(1/2):30-35.
[12]KUMAR P,SRIVASTAVA V C,MISHRA I M.Dimethyl carbonate synthesis from propylene carbonate with methanol using Cu-Zn-Al catalyst[J].Energy Fuels,2015,29(4):2664-2675.
[13]KUMAR P,SRIVASTAVA V C,MISHRA I M.Synthesis and characterization of Ce-La oxides for the formation of dimethyl carbonate by transesterification of propylene carbonate[J].Catal Commun,2015,60:27-31.
[14]LEE K H,LEE S,SHIN D,HAHM H S.Dimethyl carbonate synthesis via transesterification of ethylene carbonate and methanol using ionic liquid catalysts immobilized on mesoporous cellular foams[J].Res Chem Intermed,2016,42(1):109-121.
[15]DU G F,GUO H,WANG Y,LI W J,SHI W J,DAI B.N-heterocyclic carbene catalyzed synthesis of dimethyl carbonate via transesterification of ethylene carbonate w ith methanol[J].J Saudi Chem Soc,2015,19(1):112-115.
[16]LIAO Y H,LI F,DAI X,ZHAO N,XIAO F.Solid base catalysts derived from Ca-M-Al(M=Mg,La,Ce,Y)layered double hydroxides for dimethyl carbonate synthesis by transesterification of methanol w ith propylene carbonate[J].Chin J Catal,2017,38(11):1860-1869.
[17]UNNIKRISHNAN P,SRINIVAS D.Calcined,rare earth modified hydrotalcite as a solid,reusable catalyst for dimethyl carbonate synthesis[J].Ind Eng Chem Res,2012,51(18):6356-6363.
[18]WANG H,WANG M,ZHAO N,WEI W,SUN Y.Ca O-Zr O2Solid solution:A highly stable catalyst for the synthesis of dimethyl carbonate from propylene carbonate and methanol[J].Catal Lett,2005,105(3/4):253-257.
[19]WANG J,HAN L,WANG S,ZHANG J,YANG Y.Magnesium aluminum spinel as an acid-base catalyst for transesterification of diethyl carbonate w ith dimethyl carbonate[J].Catal Lett,2014,144(9):1602-1608.
[20]WANG L,WANG Y,LIU S,LU L,MA X,DENG Y.Efficient synthesis of dimethyl carbonate via transesterification of ethylene carbonate w ith methanol over binary zinc-yttrium oxides[J].Catal Commun,2011,16(1):45-49.
[21]XU J,LONG K Z,WU F,XUE B,LI Y X,CAO Y.Efficient synthesis of dimethyl carbonate via transesterification of ethylene carbonate over a new mesoporous ceria catalyst[J].Appl Catal A:Gen,2014,484:1-7.
[22]WU X,KANG M,ZHAO N,WEI W,SUN Y.Dimethyl carbonate synthesis over Zn O-Ca O bi-functional catalysts[J].Catal Commun,2014,46:46-50.
[23]LI H,GAO D,GAO P,WANG F,ZHAO N,XIAO F,WEI W,SUN Y.The synthesis of glycerol carbonate from glycerol and CO2over La2O2CO3-Zn O catalysts[J].Catal Sci Technol,2013,3:2801-2809.
[24]WANG D,ZHANG X,MA J,YU H,SHEN J,WEI W.La-modified mesoporous Mg-Al mixed oxides:Effective and stable base catalysts for the synthesis of dimethyl carbonate from methyl carbamate and methanol[J].Catal Sci Technol,2016,6:1530-1545.
[25]SINGH D,REDDY B,GANESH A,MAHAJANI S.Zinc/lanthanum mixed-oxide catalyst for the synthesis of glycerol carbonate by transesterification of glycerol[J].Ind Eng Chem Res,2014,53(49):18786-18795.
[26]YAN S,KIM M,SALLEY S O,.NG K Y S.Oil transesterification over calcium oxides modified with lanthanum[J].Appl Catal A:Gen,2009,360(2):163-170.
[27]WANG H,WANG M,ZHANG W,ZHAO N,WEI W,SUN Y.Synthesis of dimethyl carbonate from propylene carbonate and methanol using Ca O-Zr O2solid solutions as highly stable catalysts[J].Catal Today,2006,115(1/4):107-110.
[28]MURUGAN C,BAJAJ H C,JASRA R V.Transesterification of propylene carbonate by methanol using KF/Al2O3as an efficient base catalyst[J].Catal Lett,2010,137(3/4):224-231.
[29]MALYAADRI M,JAGADEESWARAIAH K,PRASAD P S S,LINGAIAH N.Synthesis of glycerol carbonate by transesterification of glycerol w ith dimethyl carbonate over M g/Al/Zr catalysts[J].Appl Catal A:Gen,2011,401(1/2):153-157.
[30]JIN L,ZHANG Y,DOMBROWSKI J P,CHEN C H,PRAVATAS A,XU L,PERKINS C,SUIB S L.Zn O/La2O2CO3layered composite:A new heterogeneous catalyst for the efficient ultra-fast microw ave biofuel production[J].Appl Catal B:Environ,2011,103(1/2):200-205.
[31]PARK C,NGUYEN-PHU H,SHIN E W.Glycerol carbonation with CO2and La2O2CO3/Zn O catalysts prepared by tw o different methods:Preferred reaction route depending on crystalline structure[J].M ol Catal,2017,435:99-109.
[32]JOE W,LEE H J,HONG U G,AHN Y S,SONG C J,KWON B J,SONG I K.Urea methanolysis to dimethyl carbonate over Zn O-Ce O2-M O(M O:La2O3,Y2O3,Co2O3,Ga2O3,and Zr O2)catalysts[J].J Ind Eng Chem,2012,18(5):1730.
[2]TAN H Z,WANG Z Q,XU Z N SUN J,XU Y P,CHEN Q S,CHEN Y M,GUO G C.Review on the synthesis of dimethyl carbonate[J].Catal Today,2018,https://doi.org/10.1016/j.cattod.2018.02.021.
[3]WU X,KANG M,YIN Y,WANG F,ZHAO N,XIAO F,WEI W,SUN Y.Synthesis of dimethyl carbonate by urea alcoholysis over Zn/Al bi-functional catalysts[J].Appl Catal A:Gen,2014,473:13-20.
[4]FILIPPIS P D,SCARSELLA M,BORGIANNI C,POCHETTI F.Production of dimethyl carbonate via alkylene carbonate transesterification catalyzed by basic salts[J].Energy Fuels,2006,20(1):17-20.
[5]ETA V,MAKI-ARVELA P,SALMINEN E,SALMI T,MURZIN D Y,MIKKOLA J P.The effect of alkoxide ionic liquids on the synthesis of dimethyl carbonate from CO2and methanol over Zr O2-M g O[J].Catal Lett,2011,141:1254-1261.
[6]REN M,REN J,HAO P,YANG J,WANG D,PEI Y,LIN J,LI Z.Influence of microwave irradiation on the structural properties of carbonsupported hollow copper nanoparticles and their effect on the synthesis of dimethyl carbonate[J].Chem Cat Chem,2016,8(4):861-871.
[7]SAADA R,ABOELAZAYEM O,KELLICI S,HEIL T,MORGAN D,LAMPRONTI G I,SAHA B.Greener synthesis of dimethyl carbonate using a novel tin-zirconia/graphene nanocomposite catalyst[J].Appl Catal B:Environ,2018,226:451-462.
[8]SANKAR M,SATAV S,MANIKANDAN P.Transesterification of cyclic carbonates to dimethyl carbonate using solid oxide catalyst at ambient conditions:Environmentally benign synthesis[J].Chem Sus Chem,2010,3(5):575-578.
[9]TAMBOLI A H,CHAUGULE A A,KIM H.Catalytic developments in the direct dimethyl carbonate synthesis from carbon dioxide and methanol[J].Chem Eng J,2017,323:530-544.
[10]JAGTAP S R,BHOR M D,BHANAGE B M.Synthesis of dimethyl carbonate via transesterification of ethylene carbonate with methanol using poly-4-vinyl pyridine as a novel base catalyst[J].Catal Commun,2008,9(9):1928-1931.
[11]ABIMANYU H,KIM C S,AHN B S,YOO K S.Synthesis of dimethyl carbonate by transesterification with various Mg O-Ce O2mixed oxide catalysts[J].Catal Lett,2007,118(1/2):30-35.
[12]KUMAR P,SRIVASTAVA V C,MISHRA I M.Dimethyl carbonate synthesis from propylene carbonate with methanol using Cu-Zn-Al catalyst[J].Energy Fuels,2015,29(4):2664-2675.
[13]KUMAR P,SRIVASTAVA V C,MISHRA I M.Synthesis and characterization of Ce-La oxides for the formation of dimethyl carbonate by transesterification of propylene carbonate[J].Catal Commun,2015,60:27-31.
[14]LEE K H,LEE S,SHIN D,HAHM H S.Dimethyl carbonate synthesis via transesterification of ethylene carbonate and methanol using ionic liquid catalysts immobilized on mesoporous cellular foams[J].Res Chem Intermed,2016,42(1):109-121.
[15]DU G F,GUO H,WANG Y,LI W J,SHI W J,DAI B.N-heterocyclic carbene catalyzed synthesis of dimethyl carbonate via transesterification of ethylene carbonate w ith methanol[J].J Saudi Chem Soc,2015,19(1):112-115.
[16]LIAO Y H,LI F,DAI X,ZHAO N,XIAO F.Solid base catalysts derived from Ca-M-Al(M=Mg,La,Ce,Y)layered double hydroxides for dimethyl carbonate synthesis by transesterification of methanol w ith propylene carbonate[J].Chin J Catal,2017,38(11):1860-1869.
[17]UNNIKRISHNAN P,SRINIVAS D.Calcined,rare earth modified hydrotalcite as a solid,reusable catalyst for dimethyl carbonate synthesis[J].Ind Eng Chem Res,2012,51(18):6356-6363.
[18]WANG H,WANG M,ZHAO N,WEI W,SUN Y.Ca O-Zr O2Solid solution:A highly stable catalyst for the synthesis of dimethyl carbonate from propylene carbonate and methanol[J].Catal Lett,2005,105(3/4):253-257.
[19]WANG J,HAN L,WANG S,ZHANG J,YANG Y.Magnesium aluminum spinel as an acid-base catalyst for transesterification of diethyl carbonate w ith dimethyl carbonate[J].Catal Lett,2014,144(9):1602-1608.
[20]WANG L,WANG Y,LIU S,LU L,MA X,DENG Y.Efficient synthesis of dimethyl carbonate via transesterification of ethylene carbonate w ith methanol over binary zinc-yttrium oxides[J].Catal Commun,2011,16(1):45-49.
[21]XU J,LONG K Z,WU F,XUE B,LI Y X,CAO Y.Efficient synthesis of dimethyl carbonate via transesterification of ethylene carbonate over a new mesoporous ceria catalyst[J].Appl Catal A:Gen,2014,484:1-7.
[22]WU X,KANG M,ZHAO N,WEI W,SUN Y.Dimethyl carbonate synthesis over Zn O-Ca O bi-functional catalysts[J].Catal Commun,2014,46:46-50.
[23]LI H,GAO D,GAO P,WANG F,ZHAO N,XIAO F,WEI W,SUN Y.The synthesis of glycerol carbonate from glycerol and CO2over La2O2CO3-Zn O catalysts[J].Catal Sci Technol,2013,3:2801-2809.
[24]WANG D,ZHANG X,MA J,YU H,SHEN J,WEI W.La-modified mesoporous Mg-Al mixed oxides:Effective and stable base catalysts for the synthesis of dimethyl carbonate from methyl carbamate and methanol[J].Catal Sci Technol,2016,6:1530-1545.
[25]SINGH D,REDDY B,GANESH A,MAHAJANI S.Zinc/lanthanum mixed-oxide catalyst for the synthesis of glycerol carbonate by transesterification of glycerol[J].Ind Eng Chem Res,2014,53(49):18786-18795.
[26]YAN S,KIM M,SALLEY S O,.NG K Y S.Oil transesterification over calcium oxides modified with lanthanum[J].Appl Catal A:Gen,2009,360(2):163-170.
[27]WANG H,WANG M,ZHANG W,ZHAO N,WEI W,SUN Y.Synthesis of dimethyl carbonate from propylene carbonate and methanol using Ca O-Zr O2solid solutions as highly stable catalysts[J].Catal Today,2006,115(1/4):107-110.
[28]MURUGAN C,BAJAJ H C,JASRA R V.Transesterification of propylene carbonate by methanol using KF/Al2O3as an efficient base catalyst[J].Catal Lett,2010,137(3/4):224-231.
[29]MALYAADRI M,JAGADEESWARAIAH K,PRASAD P S S,LINGAIAH N.Synthesis of glycerol carbonate by transesterification of glycerol w ith dimethyl carbonate over M g/Al/Zr catalysts[J].Appl Catal A:Gen,2011,401(1/2):153-157.
[30]JIN L,ZHANG Y,DOMBROWSKI J P,CHEN C H,PRAVATAS A,XU L,PERKINS C,SUIB S L.Zn O/La2O2CO3layered composite:A new heterogeneous catalyst for the efficient ultra-fast microw ave biofuel production[J].Appl Catal B:Environ,2011,103(1/2):200-205.
[31]PARK C,NGUYEN-PHU H,SHIN E W.Glycerol carbonation with CO2and La2O2CO3/Zn O catalysts prepared by tw o different methods:Preferred reaction route depending on crystalline structure[J].M ol Catal,2017,435:99-109.
[32]JOE W,LEE H J,HONG U G,AHN Y S,SONG C J,KWON B J,SONG I K.Urea methanolysis to dimethyl carbonate over Zn O-Ce O2-M O(M O:La2O3,Y2O3,Co2O3,Ga2O3,and Zr O2)catalysts[J].J Ind Eng Chem,2012,18(5):1730.