Ce改性硅钨酸催化制备月桂酸单甘酯
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摘要
采用离子交换法合成多种稀土改性硅钨酸催化剂M_xH_(4–3x)SiW_(12)O_(40)(M=La, Ce, Pr, Nd, Sm; x=1/3, 2/3, 1,4/3),并利用FTIR、 XRD、 TGA-DTG、固体核磁共振结合探针分子技术(31P-TMPOMAS-NMR)对Ce_xH_(4–3x)SiW_(12)O_(40)结构、稳定性及酸性进行了表征;结果表明,Ce1/3H3Si W12O40催化剂在月桂酸单甘酯制备中显示出最好的催化性能。稀土Ce有效结合到硅钨酸上,制备的催化剂保持了完整的Keggin结构。与纯硅钨酸相比,CexH4–3xSiW12O40的酸强度有所减弱,但由于该类催化剂较强的Br?nsted酸性及Br?nsted-Lewis酸性位间的协同效应,使Ce_xH_(4–3x)SiW_(12)O_(40)在月桂酸单甘酯的制备中具有良好的催化性能。以Ce_(1/3)H_3SiW_(12)O_(40)为催化剂,在甘油/月桂酸物质的量比为4、催化剂用量为月桂酸质量的4%、反应温度423 K、反应时间120 min下,月桂酸单甘酯产率为78.4%;动力学研究表明,该反应活化能为42.37 kJ/mol;Ce_(1/3)H_3SiW_(12)O_(40)催化剂经5次回收利用后,月桂酸单甘酯的产率为71.4%,具有较好的重复使用性能。
A series of rare earth elements modified tungstosilicic acid catalysts Ce_xH_(4–3x)SiW_(12)O_(40)(M=La,Ce,Pr,Nd,Sm;x=1/3,2/3,1,4/3) were prepared by ion exchange method.The structure,stability and acidity of Ce_xH_(4–3x)SiW_(12)O_(40) catalysts were characterized by FTIR,XRD,TGA-DTG and solid-state 31 P-TMPO MAS-NMR spectra of adsorbed trimethylphosphine oxide(31 P-TMPO MAS-NMR).The results showed that Ce_(1/3)H_3SiW_(12)O_(40) catalyst had the best catalytic activity in the synthesis of glycerol monolaurate(GML).Rare earth element cerium effectively bound to tungstosilicic acid,which made the prepared catalyst maintain a complete Keggin structure.Although the acidity of CexH4–3xSiW12O40 catalysts decreased compared with that of tungstosilicic acid,the catalysts exhibited good catalytic activities during the esterification due to strong Br?nsted acidity and Br?nsted-Lewis acid synergy.When the molar ratio of glycerol(GL) to lauric acid(LA) was 4.0,the mass fraction of Ce_(1/3)H_3SiW_(12)O_(40) catalyst was 4%(based on LA),the reaction temperature was 423 K,and the reaction time was 120 min,the yield of GML was 78.4%.Kinetic studies revealed that the apparent activation energy of the reaction was 42.37 kJ/mol.The yield of GML could still reach 71.4% after Ce_(1/3)H_3SiW_(12)O_(40) catalyst was reused for 5 times,indicating that this catalyst had excellent reuse ability.
A series of rare earth elements modified tungstosilicic acid catalysts Ce_xH_(4–3x)SiW_(12)O_(40)(M=La,Ce,Pr,Nd,Sm;x=1/3,2/3,1,4/3) were prepared by ion exchange method.The structure,stability and acidity of Ce_xH_(4–3x)SiW_(12)O_(40) catalysts were characterized by FTIR,XRD,TGA-DTG and solid-state 31 P-TMPO MAS-NMR spectra of adsorbed trimethylphosphine oxide(31 P-TMPO MAS-NMR).The results showed that Ce_(1/3)H_3SiW_(12)O_(40) catalyst had the best catalytic activity in the synthesis of glycerol monolaurate(GML).Rare earth element cerium effectively bound to tungstosilicic acid,which made the prepared catalyst maintain a complete Keggin structure.Although the acidity of CexH4–3xSiW12O40 catalysts decreased compared with that of tungstosilicic acid,the catalysts exhibited good catalytic activities during the esterification due to strong Br?nsted acidity and Br?nsted-Lewis acid synergy.When the molar ratio of glycerol(GL) to lauric acid(LA) was 4.0,the mass fraction of Ce_(1/3)H_3SiW_(12)O_(40) catalyst was 4%(based on LA),the reaction temperature was 423 K,and the reaction time was 120 min,the yield of GML was 78.4%.Kinetic studies revealed that the apparent activation energy of the reaction was 42.37 kJ/mol.The yield of GML could still reach 71.4% after Ce_(1/3)H_3SiW_(12)O_(40) catalyst was reused for 5 times,indicating that this catalyst had excellent reuse ability.
引文
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[20]Luzgin M V,Kazantsev M S,Volkova G G,et al.Solid-state NMRstudy of the kinetics and mechanism of dimethyl ether carbonylation on cesium salt of 12-tungstophosphoric acid modified with Ag,Pt,and Rh[J].Journal of Catalysis,2013,308(1):250-257.
[21]Izumi Y,Ono M,Ogawa M,et al.Acidic cesium salts of Keggin-type heteropolytungstic acids as insoluble solid acid catalysts for esterification and hydrolysis reactions[J].Chemistry Letters,1993,22(5):825-828.
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[23]Zhu S H,Gao X Q,Dong F,et al.Design of a highly active silverexchanged phosphotungstic acid catalyst for glycerol esterification with acetic acid[J].Journal of Catalysis,2013,306:155-163.
[24]SHU Qing(舒庆),HOU Xiaopeng(侯小鹏).Research progress of the application of solid catalysts with rare earth in the synthesis of biodiesel[J].Chemical Industry and Engineering Progress(化工进展),2016,35(2):493-498.
[25]Cao Zhengtai(曹正太),Liu Shizhong(柳士忠).Study on the synthesis of butyl acetate catalyzed by rare earth salts of heteropoly acid[J].Huibei Chemical Industry(湖北化工),1999,(4):7-8.
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[27]Okuhara T,Watanabe H,Nishimura T,et al.Microstructure of cesium hydrogen salts of 12-tungstophosphoric acid relevant to novel acid catalysts[J].Chemistry of Materials,2000,12(8):2230-2238.
[28]Hu Guodong(胡国栋),Wu Qingyin(吴庆银).Catalytic chemical characteristics of heteropoly acid-pseudo liquid phase catalysis[J].Liaoning Chemical Industry(辽宁化工),1991,(4):14-19.
[29]Peng Baoxiang(彭宝祥),Shu Qing(舒庆),Wang Guangrun(王光润),et al.Kinetics of esterification for acid-catalyzed preparation of biodiesel[J].Chemical Reaction Engineering and Technology(化学反应工程与工艺),2009,25(3):250-255.
[30]Tesser R,Serio M Di,Guida M,et al.Kinetics of oleic acid esterification with methanol in the presence of triglycerides[J].Industrial and Engineering Chemistry Research,2005,44(21):7978-7982.
[31]Parida K M,Mallick S.Silicotungstosilicic acid supported zirconia:an effective catalyst for esterification reaction[J].Journal of Molecular Catalysis A Chemical,2007,275(1/2):77-83.
[32]Zheng Xiucheng(郑修成),Wu Min(吴敏),Chen Ya(陈雅),et al.One-pot synthesis of silicotungstic acid-SBA-15 mesoporous solid acids and applications in the esterification of oleic acid with methanol[J].Journal of Xinyang Normal University(信阳师范学院学报),2016,29(3):417-421.
[33]Oliveira C F,Dezaneti L M,Garcia F A C,et al.Esterification of oleic acid with ethanol by 12-tungstophosphoric acid supported on zirconia[J].Applied of Catalysis A General,2010,372(2):153-161.
[34]Zheng A M,Zhang H L,Lu X,et al.Theoretical predictions of31PNMR chemical shift threshold of trimethylphosphine oxide absorbed on solid acid catalysts[J].Journal of Physical Chemistry B,2008,112(15):4496-4505.
[35]Huang S J,Yang C Y,Zheng A,et al.New insights into keggin-type12-tungstophosphoric acid from 31P MAS-NMR analysis of absorbed trimethylphosphine oxide and DFT calculations[J].Chem Asian J,2011,6(1):137-148.
[36]Zheng A,Huang S J,Liu S B,et al.Acid properties of solid acid catalysts characterized by solid-state 31PNMR of adsorbed phosphorous probe molecules[J].Physical Chemistry Chemical Physics,2011,13(33):14889-14901.
[37]You Liqin(游利琴),Wang Hongyan(王宏雁).Study on catalytic synthesis of glycerol monolaurate by solid superacid[J].Science and Technology of Cereals,Oils and Foods(粮油食品科技),2012,20(4):54-56.
[38]Wang Song(王松),Zhang Zhenyan(张争艳),Chang Qianqian(常欠欠),et al.Synthesis of glycerol monolaurate using functionalized ionic liquids catalysts[J].CIESC Journal(化工学报),2015,66(S1):209-215.
[2]Hess D J,Henry-Stanley M J,Wells C L.Antibacterial synergy of glycerol monolaurate and aminoglycosides in Staphylococcus aureus biofilms[J].Antimicrobial Agents&Chemotherapy,2014,58(11):6970-6973.
[3]Jiang Zengliang(蒋增良),Yang Ming(杨明),Du Juan(杜鹃),et al.Antibacterial and antiviral properties of glycerol monolaurate and its application in food[J].Journal of the Chinese Cereals and Oils Association(中国粮油学报),2015,30(2):142-145.
[4]Liang Zhunchen(梁准成),Yang Jiguo(杨继国),Liu Dongqi(刘冬蕲),et al.Synthesis and antibacterial activity of lauric acid derivatives[J].Modern Food Science and Technology,2015,31(3):84-90.
[5]Deng Yingying(邓颖颖),Yang Na(杨哪),Xu Xueming(徐学明).Aspergillus niger lipase-catalyzed synthesis of high content lauric acid monoglyceride[J].Science and Technology of Food Industry(食品工业科技),2012,33(9):209-211.
[6]Huang Fang(黄芳),Liu Bo(刘波).Syntheses of glycerol monolaurate[J].Journal of Liaodong University(Natural Sciences)(辽东学院学报:自然科学版),2007,14(2):122-124.
[7]Song Guosheng(宋国胜),Guo Siyuan(郭祀远),Cai Miaoyan(蔡妙颜),et al.Synthesis of glycerol monolaurate catalyzed by ion exchange resin[J].China of Oils and Fats(中国油脂),2001,26(5):89-90.
[8]Han X X,Zhang X X,Zhu G Q,et al.Ionic liquid-silicotungstic acid composites as efficient and recyclable catalysts for the selective esterification of glycerol with lauric acid to monolaurin[J].ChemCatChem,2017,9(14):2727-2738.
[9]Xian Shujuan(缐述娟),Wu Xiaowei(武小伟),Zhao Haisheng(赵海生).Progress in research on esterification reactions catalyzed by heteropolyacid[J].China Science&Technology Panorama Magazine(中国科技纵横),2014,(10):263-264.
[10]Li Weiyuan(李威渊),Liu Yuanyuan(刘媛媛),Zheng Huayan(郑华艳),et al.Molecular structure and application of heteropolyacid(salt)catalysts for organic synthesis[J].Chemical Industry and Engineering Progress(化工进展),2010,29(2):243-249.
[11]Shu Qing(舒庆),Liu Bao(刘宝),Song Shenghai(宋胜海),et al.Optimization of the tungsten/molybdenum mixed heteropoly acid salt-catalyzed esterification reaction conditions[J].Nonferrous Metals Science and Engineering(有色金属科学与工程),2014,5(6):21-27.
[12]Zhu S H,Zhu Y L,Gao X Q,et al.Production of bioadditives from glycerol esterification over zirconia supported heteropolyacids[J].Bioresource Technology,2013,130(1):45-51.
[13]Khayoon M S,Hameed B H.Synthesis of hybrid SBA-15functionalized with molybdophosphoric acid as efficient catalyst for glycerol esterification to fuel additives[J].Applied of Catalysis AGeneral,2012,433/434:152-161.
[14]Liu Shirong(刘士荣),Li Ce(李策).Synthesis of glyceryl triacetate catalyzed by tungstophosphoric acid supported on actived carbon[J].Journal of Southern Yangtze University(Natural Science Edition)(江南大学学报:自然科学版),2004,3(4):411-414.
[15]Jiang Chuntao(江春涛),Li Meng(李猛),Yang Hui(杨惠),et al.Catalytic synthesis of n-butyl acetate with attapulgite supported phosphotungstic acid[J].Guang Dong Chemical Industry(广东化工),2013,40(5):1-2.
[16]Fan Zongliang(范宗良),Qi Wenjuan(漆文娟),Li Guixian(李贵贤),et al.Advance in studies of supporged heteropolyacid catalysts for esterification reaction[J].Petrochemical Technology&Application(石化技术与应用),2014,32(4):361-365.
[17]Han X X,Chen K K,Du H,et al.Novel Keggin-type H4PVMo11O40-based ionic liquid catalysts for n-caprylic acid esterification[J].Journal of Taiwan Institute of Chemical Engineers,2016,58:203-209.
[18]Han X X,Chen K K,Yan W,et al.Amino acid-functionalized heteropolyacids as efficient and recyclable catalysts for esterification of palmitic acid to biodiesel[J].Fuel,2016,165:115-122.
[19]Shu Qing(舒庆),Hou Xiaopeng(侯小鹏),Liu Fengsheng(刘峰生),et al.Catalytic activity of La-modified phosphotungstic heteropoly acid salt in synthesis of biodiesel from esterification of methanol and oleci acid[J].Nonferrous Metals Science and Engineering(有色金属科学与工程),2016,7(3):131-136.
[20]Luzgin M V,Kazantsev M S,Volkova G G,et al.Solid-state NMRstudy of the kinetics and mechanism of dimethyl ether carbonylation on cesium salt of 12-tungstophosphoric acid modified with Ag,Pt,and Rh[J].Journal of Catalysis,2013,308(1):250-257.
[21]Izumi Y,Ono M,Ogawa M,et al.Acidic cesium salts of Keggin-type heteropolytungstic acids as insoluble solid acid catalysts for esterification and hydrolysis reactions[J].Chemistry Letters,1993,22(5):825-828.
[22]Pathan S,Patel A.Solvent free clean selective oxidation of alcohols catalyzed by mono transition metal(Co,Mn,Ni)-substituted Kegginphosphomolybdates using hydrogen peroxide[J].Applied of Catalysis A General,2013,459(9):59-64.
[23]Zhu S H,Gao X Q,Dong F,et al.Design of a highly active silverexchanged phosphotungstic acid catalyst for glycerol esterification with acetic acid[J].Journal of Catalysis,2013,306:155-163.
[24]SHU Qing(舒庆),HOU Xiaopeng(侯小鹏).Research progress of the application of solid catalysts with rare earth in the synthesis of biodiesel[J].Chemical Industry and Engineering Progress(化工进展),2016,35(2):493-498.
[25]Cao Zhengtai(曹正太),Liu Shizhong(柳士忠).Study on the synthesis of butyl acetate catalyzed by rare earth salts of heteropoly acid[J].Huibei Chemical Industry(湖北化工),1999,(4):7-8.
[26]Han X X,Kuang Y Y,Ouyang K,et al.Role of acidity over rare earth metal ion-exchanged heteropoly tungstates during oxidation of alcohols[J].Journal of the Taiwan Institute of Chemical Engineers,2017,70:23-31.
[27]Okuhara T,Watanabe H,Nishimura T,et al.Microstructure of cesium hydrogen salts of 12-tungstophosphoric acid relevant to novel acid catalysts[J].Chemistry of Materials,2000,12(8):2230-2238.
[28]Hu Guodong(胡国栋),Wu Qingyin(吴庆银).Catalytic chemical characteristics of heteropoly acid-pseudo liquid phase catalysis[J].Liaoning Chemical Industry(辽宁化工),1991,(4):14-19.
[29]Peng Baoxiang(彭宝祥),Shu Qing(舒庆),Wang Guangrun(王光润),et al.Kinetics of esterification for acid-catalyzed preparation of biodiesel[J].Chemical Reaction Engineering and Technology(化学反应工程与工艺),2009,25(3):250-255.
[30]Tesser R,Serio M Di,Guida M,et al.Kinetics of oleic acid esterification with methanol in the presence of triglycerides[J].Industrial and Engineering Chemistry Research,2005,44(21):7978-7982.
[31]Parida K M,Mallick S.Silicotungstosilicic acid supported zirconia:an effective catalyst for esterification reaction[J].Journal of Molecular Catalysis A Chemical,2007,275(1/2):77-83.
[32]Zheng Xiucheng(郑修成),Wu Min(吴敏),Chen Ya(陈雅),et al.One-pot synthesis of silicotungstic acid-SBA-15 mesoporous solid acids and applications in the esterification of oleic acid with methanol[J].Journal of Xinyang Normal University(信阳师范学院学报),2016,29(3):417-421.
[33]Oliveira C F,Dezaneti L M,Garcia F A C,et al.Esterification of oleic acid with ethanol by 12-tungstophosphoric acid supported on zirconia[J].Applied of Catalysis A General,2010,372(2):153-161.
[34]Zheng A M,Zhang H L,Lu X,et al.Theoretical predictions of31PNMR chemical shift threshold of trimethylphosphine oxide absorbed on solid acid catalysts[J].Journal of Physical Chemistry B,2008,112(15):4496-4505.
[35]Huang S J,Yang C Y,Zheng A,et al.New insights into keggin-type12-tungstophosphoric acid from 31P MAS-NMR analysis of absorbed trimethylphosphine oxide and DFT calculations[J].Chem Asian J,2011,6(1):137-148.
[36]Zheng A,Huang S J,Liu S B,et al.Acid properties of solid acid catalysts characterized by solid-state 31PNMR of adsorbed phosphorous probe molecules[J].Physical Chemistry Chemical Physics,2011,13(33):14889-14901.
[37]You Liqin(游利琴),Wang Hongyan(王宏雁).Study on catalytic synthesis of glycerol monolaurate by solid superacid[J].Science and Technology of Cereals,Oils and Foods(粮油食品科技),2012,20(4):54-56.
[38]Wang Song(王松),Zhang Zhenyan(张争艳),Chang Qianqian(常欠欠),et al.Synthesis of glycerol monolaurate using functionalized ionic liquids catalysts[J].CIESC Journal(化工学报),2015,66(S1):209-215.