负载型HMCM-22/PW分子筛催化合成十二烷基磷酸酯
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摘要
用磷钨酸(PW)以浸渍法改性HMCM-22分子筛,并用X射线衍射、扫描电子显微镜、红外光谱对催化剂进行表征。结果表明,改性后的HMCM-22分子筛原有的结构和特征未发生变化;在应用于十二醇与五氧化磷(P_2O_5)摩尔比为2∶1的合成单十二烷基酯化反应中,产物中单酯的选择性有了显著的提高,说明PW与HMCM-22分子筛的活性中心发生了协同作用促进了酯化反应的进行,同时也表明该催化剂有优良的催化性能;在催化剂用量为总反应物的1.5%,加水的量为6.5%,PW的负载量为4%,反应温度为90℃,反应时间为4 h的条件下单酯的选择性达90%。
The HMCM-22 molecular sieve was modified with phosphotungstic acid(PW) by an impregnation method, and the resulting composite catalysts were characterized by XRD, SEM, FT-IR.The results indicated that there was no change in the original structure and characteristics of the modified HMCM-22 molecular sieve. The productivity of monododecyl ester was improved significantly for the synthesis of mono-alkyl phosphate(MPA) through esterification of dodecanol and phosphorus pentoxide at a molar ration of 2/1,indicating that the esterification was promoted synergistically by the active center of composite catalysts, thus resulting in excellent catalytic performance. For the composite catalyst loaded with 4 wt % PW, a high productivity of 90 %was achieved when the amount of water was 9 g,the amount of composites catalysts in total reactants was 1.5 wt %, the reaction temperature was set at 90 ℃, and the reaction time was set as 4 h. This suggests that the PW/HMCM-22 composite molecular sieve has an excellent catalytic effect.
The HMCM-22 molecular sieve was modified with phosphotungstic acid(PW) by an impregnation method, and the resulting composite catalysts were characterized by XRD, SEM, FT-IR.The results indicated that there was no change in the original structure and characteristics of the modified HMCM-22 molecular sieve. The productivity of monododecyl ester was improved significantly for the synthesis of mono-alkyl phosphate(MPA) through esterification of dodecanol and phosphorus pentoxide at a molar ration of 2/1,indicating that the esterification was promoted synergistically by the active center of composite catalysts, thus resulting in excellent catalytic performance. For the composite catalyst loaded with 4 wt % PW, a high productivity of 90 %was achieved when the amount of water was 9 g,the amount of composites catalysts in total reactants was 1.5 wt %, the reaction temperature was set at 90 ℃, and the reaction time was set as 4 h. This suggests that the PW/HMCM-22 composite molecular sieve has an excellent catalytic effect.
引文
[1] 王姗姗.长碳链磷酸酯表面活性剂的制备与性能研究[D].衡阳:南华大学,2014.
[2] 巴琰.烷基磷酸酯的合成及表面性能研究[D].大连:大连理工大学,2005.
[3] 夏婷.纺丝油剂用磷酸酯型抗静电剂合成反应机理研究[D].杭州:浙江大学,2008.
[4] 刘琳,钱建华,仲崇民.烷基磷酸酯的合成[J].精细石油化工,1999,11(5):45-47.LIU L,QIAN J H,ZHONG C M.Synthesis of Alkyl Phosphate[J].Fine Petrochemical Industry,1999,11 (5):45-47.
[5] 沈磊,任晓乾,熊剑琴,等.月桂醇高选择性酯化合成单十二烷基磷酸酯[J].日用化学工业,2008,38(6):345-348.SHEN L,REN X Q,XIONG J Q,et al.Synthesis of Monododecyl Phosphate by High Selective Esterification of Lauryl Alcohol[J].Daily Chemical Industry,2008,38 (6):345-348.
[6] 牛雄雷.MCM-22分子筛的合成与应用研究[D].大连:中国科学院研究生院(大连化学物理研究所),2006.
[7] 张文飞,梁金花,刘艳秋,等.酸碱双功能MgO/HMCM-22催化剂上Knoevenagel缩合反应[J].催化学报,2013,34(3):559-566.ZHANG W F,LIANG J H,LIU Y Q,et al.Knoevenagel Condensation over Acid-base Bifunctional MgO/HMCM-22 Catalyst[J].Journal of Catalysis,2013,34 (3):559-566.
[8] 李宁,梁金花,张文飞,等.Ca/HMCM-22复合分子筛上烷基磷酸酯的绿色合成[J].高校化学工程学报,2012,26(6):971-976.LI N,LIANG J H,ZHANG W F,et al.Green Synthesis of Alkyl Phosphate on Ca/HMCM-22 Composite Molecular Sieve[J].Journal of Chemical Engineering of Colleges and Universities,2012,26 (6):971-976.
[9] 赵丽萍,赵丽杰.电位滴定法测定十二烷基磷酸酯[J].广西化工,2000,12(2):46-49.ZHAO L P,ZHAO L J.Determination of Dodecyl Phosphate by Potentiometric[J].Titration.Guangxi Chemical,2000,12 (2):46-49.
[10] 何文猛,王清成,刘建祥,等.共沸脱水法烷基磷酸酯的合成[J].西南工学院学报,1997,12(4):71-75.HE W M,WANG Q C,LIU J X,et al.Synthesis of Alkyl Phosphate Ester by Azeotropic Dehydration[J].Journal of Southwest Institute of Technology,1997,12 (4):71-75.
[11] CORMA A,CORELL C,FOMéS V,et al.Infrared Spectroscopy,Thermoprogrammed Desorption,and Nuclear Magnetic Resonance Study of the Acidity,Structure,and Stability of Zeolite MCM-22[J].Zeolite,1995,15(7):907-912
[12] 孙渝,乐英红,李惠云,等.MCM-41负载磷钨杂多酸催化剂的性能研究[J].化学学报,1999(7):746-753.SUN Y,LE Y H,LI H Y,et al.Study on the Performance of MCM-41 Supported Phosphotungstic Heteropolyacid Catalyst[J].Journal of Chemistry,1999 (7):746-753.
[13] DEEPTI J,ASHU R.Mgo Enriched Coal Fly Ash as Highly Active Heterogencous Base Catalyst for Claisen-schmidt Condensation Reaction[J].American Chemical Science Journal.2011,1(2):37-49.
[14] KUROSAKI T,FURUGAKI H,MATSUNAGA A,et al.Studies on Phosphorylation I,Phosphorylation of Alcohol with Phosphorus Pentoxide in the Presence of Water[J].Yukagaku,1990,39(4):250-258.
[15] 叶庆国,王晟.烷基磷酸酯的合成及动力学研究[J].青岛科技大学学报,2006,27(5):298-398.YE Q G,WANG S.Synthesis and Kinetics of Alkyl Phosphate[J].Journal of Qingdao University of Science and Technology,2006,27 (5):298-398.
[16] 胡卫东,严春艳.磷酸酯表面活性剂的合成[J].表面活性剂工业,1997(4):15-17.HU W D,YAN C Y.Synthesis of Phosphate Surfactant[J].Surfactant Industry,1997 (4):15-17.
[17] 张澜萃,陈楠,李晓辉,等.负载型杂多酸催化合成十二烷基磷酸酯[J].辽宁师范大学学报(自然科学版),2005(4):436-437.ZHANG L C,CHEN N,LI X H,et al.Synthesis of Dodecyl Phosphate Ester Catalyzed by Supported Heteropolyacid[J].Journal of Liaoning normal University (Natural Science Edition),2005 (4):436-437.
[18] AYYAMPERUMAL S,KENICHI K,HUANG S J,et al.Calcium-Incorporated Mesoporous Aluminosilicates:Synthesis,Characterization,and Applications to the Condensation of Long-chain Fatty Acid with Long-chain Amine and Alcohol[J].Ind Eng Chem Res,2010,49(1):65-71.
[19] 陈永礼,宋代磊,王润霞,等.磷钨酸铝催化合成十二烷基磷酸单酯[J].工业催化,2009,17(6):66-69.CHEN Y L,SONG D L,WANG R X,et al.Synthesis of Dodecyl Phosphate Monoester Catalyzed by Aluminum Phosphotungstate[J].Industrial Catalysis,2009,17 (6):66-69.
[20] 郭春伟.烷基磷酸酯的合成及性能研究[D].无锡:江南大学,2005.
[21] HIMMELREICH U,DOBSON G P.Detection and Quantification of Free Cytosolic Inorganic Phosphate and Other Phosphorus Metebolitesin the Beating Mouse Heart Muscle In Situ NMR in Biomedicine[J].American Chemical Science Journal,2000,13:467-473.
[22] 张玉华,彭勤纪.磷酸酯类阴离子表面活性剂的～(31)P-NMR波谱分析[J].分析测试学报,1995(4):16-21.ZHANG Y H,PENG Q J.(31) P-NMR Spectrum Ana-lysis of Phosphate Anionic Surfactants[J].Journal of Analytical Testing,1995 (4):16-21.
[23] GORENSTEIN G D,WYRWIC M A,BODE J.Phosphorus-31NMR Principles and Applications[M].Orlando:Academic Press INC,1984:323-329.
[24] 闫秀云,曹俊仲,姜滇.有机膦酸酯衍生物～(31)P NMR波谱[C]//第六届全国波谱学学术会议论文摘要集.中国物理学会波谱学专业委员会,1990:2.
[2] 巴琰.烷基磷酸酯的合成及表面性能研究[D].大连:大连理工大学,2005.
[3] 夏婷.纺丝油剂用磷酸酯型抗静电剂合成反应机理研究[D].杭州:浙江大学,2008.
[4] 刘琳,钱建华,仲崇民.烷基磷酸酯的合成[J].精细石油化工,1999,11(5):45-47.LIU L,QIAN J H,ZHONG C M.Synthesis of Alkyl Phosphate[J].Fine Petrochemical Industry,1999,11 (5):45-47.
[5] 沈磊,任晓乾,熊剑琴,等.月桂醇高选择性酯化合成单十二烷基磷酸酯[J].日用化学工业,2008,38(6):345-348.SHEN L,REN X Q,XIONG J Q,et al.Synthesis of Monododecyl Phosphate by High Selective Esterification of Lauryl Alcohol[J].Daily Chemical Industry,2008,38 (6):345-348.
[6] 牛雄雷.MCM-22分子筛的合成与应用研究[D].大连:中国科学院研究生院(大连化学物理研究所),2006.
[7] 张文飞,梁金花,刘艳秋,等.酸碱双功能MgO/HMCM-22催化剂上Knoevenagel缩合反应[J].催化学报,2013,34(3):559-566.ZHANG W F,LIANG J H,LIU Y Q,et al.Knoevenagel Condensation over Acid-base Bifunctional MgO/HMCM-22 Catalyst[J].Journal of Catalysis,2013,34 (3):559-566.
[8] 李宁,梁金花,张文飞,等.Ca/HMCM-22复合分子筛上烷基磷酸酯的绿色合成[J].高校化学工程学报,2012,26(6):971-976.LI N,LIANG J H,ZHANG W F,et al.Green Synthesis of Alkyl Phosphate on Ca/HMCM-22 Composite Molecular Sieve[J].Journal of Chemical Engineering of Colleges and Universities,2012,26 (6):971-976.
[9] 赵丽萍,赵丽杰.电位滴定法测定十二烷基磷酸酯[J].广西化工,2000,12(2):46-49.ZHAO L P,ZHAO L J.Determination of Dodecyl Phosphate by Potentiometric[J].Titration.Guangxi Chemical,2000,12 (2):46-49.
[10] 何文猛,王清成,刘建祥,等.共沸脱水法烷基磷酸酯的合成[J].西南工学院学报,1997,12(4):71-75.HE W M,WANG Q C,LIU J X,et al.Synthesis of Alkyl Phosphate Ester by Azeotropic Dehydration[J].Journal of Southwest Institute of Technology,1997,12 (4):71-75.
[11] CORMA A,CORELL C,FOMéS V,et al.Infrared Spectroscopy,Thermoprogrammed Desorption,and Nuclear Magnetic Resonance Study of the Acidity,Structure,and Stability of Zeolite MCM-22[J].Zeolite,1995,15(7):907-912
[12] 孙渝,乐英红,李惠云,等.MCM-41负载磷钨杂多酸催化剂的性能研究[J].化学学报,1999(7):746-753.SUN Y,LE Y H,LI H Y,et al.Study on the Performance of MCM-41 Supported Phosphotungstic Heteropolyacid Catalyst[J].Journal of Chemistry,1999 (7):746-753.
[13] DEEPTI J,ASHU R.Mgo Enriched Coal Fly Ash as Highly Active Heterogencous Base Catalyst for Claisen-schmidt Condensation Reaction[J].American Chemical Science Journal.2011,1(2):37-49.
[14] KUROSAKI T,FURUGAKI H,MATSUNAGA A,et al.Studies on Phosphorylation I,Phosphorylation of Alcohol with Phosphorus Pentoxide in the Presence of Water[J].Yukagaku,1990,39(4):250-258.
[15] 叶庆国,王晟.烷基磷酸酯的合成及动力学研究[J].青岛科技大学学报,2006,27(5):298-398.YE Q G,WANG S.Synthesis and Kinetics of Alkyl Phosphate[J].Journal of Qingdao University of Science and Technology,2006,27 (5):298-398.
[16] 胡卫东,严春艳.磷酸酯表面活性剂的合成[J].表面活性剂工业,1997(4):15-17.HU W D,YAN C Y.Synthesis of Phosphate Surfactant[J].Surfactant Industry,1997 (4):15-17.
[17] 张澜萃,陈楠,李晓辉,等.负载型杂多酸催化合成十二烷基磷酸酯[J].辽宁师范大学学报(自然科学版),2005(4):436-437.ZHANG L C,CHEN N,LI X H,et al.Synthesis of Dodecyl Phosphate Ester Catalyzed by Supported Heteropolyacid[J].Journal of Liaoning normal University (Natural Science Edition),2005 (4):436-437.
[18] AYYAMPERUMAL S,KENICHI K,HUANG S J,et al.Calcium-Incorporated Mesoporous Aluminosilicates:Synthesis,Characterization,and Applications to the Condensation of Long-chain Fatty Acid with Long-chain Amine and Alcohol[J].Ind Eng Chem Res,2010,49(1):65-71.
[19] 陈永礼,宋代磊,王润霞,等.磷钨酸铝催化合成十二烷基磷酸单酯[J].工业催化,2009,17(6):66-69.CHEN Y L,SONG D L,WANG R X,et al.Synthesis of Dodecyl Phosphate Monoester Catalyzed by Aluminum Phosphotungstate[J].Industrial Catalysis,2009,17 (6):66-69.
[20] 郭春伟.烷基磷酸酯的合成及性能研究[D].无锡:江南大学,2005.
[21] HIMMELREICH U,DOBSON G P.Detection and Quantification of Free Cytosolic Inorganic Phosphate and Other Phosphorus Metebolitesin the Beating Mouse Heart Muscle In Situ NMR in Biomedicine[J].American Chemical Science Journal,2000,13:467-473.
[22] 张玉华,彭勤纪.磷酸酯类阴离子表面活性剂的～(31)P-NMR波谱分析[J].分析测试学报,1995(4):16-21.ZHANG Y H,PENG Q J.(31) P-NMR Spectrum Ana-lysis of Phosphate Anionic Surfactants[J].Journal of Analytical Testing,1995 (4):16-21.
[23] GORENSTEIN G D,WYRWIC M A,BODE J.Phosphorus-31NMR Principles and Applications[M].Orlando:Academic Press INC,1984:323-329.
[24] 闫秀云,曹俊仲,姜滇.有机膦酸酯衍生物～(31)P NMR波谱[C]//第六届全国波谱学学术会议论文摘要集.中国物理学会波谱学专业委员会,1990:2.