磺酸功能化钛纳米管催化合成乙酰丙酸正丁酯
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摘要
以水热法合成的二氧化钛纳米管为载体,将其与3-巯丙基三甲氧基硅烷、双氧水反应,制备了磺酸功能化钛纳米管催化剂(TNTs-SO_3H),采用XRD、FTIR、TEM、TG、UV-Vis及Hammett指示剂法对催化剂的结构和性能进行了表征与测试。以催化合成乙酰丙酸正丁酯为探针反应,考察了TNTs-SO_3H的催化性能。结果表明:当n(乙酰丙酸)∶n(正丁醇)=1∶5、TNTs-SO_3H用量为乙酰丙酸质量的10%、反应温度120℃、反应时间4 h时,乙酰丙酸正丁酯的收率可达86.5%,TNTs-SO_3H重复使用7次后,乙酰丙酸正丁酯收率仍达81.2%。
Titanium oxide nanotubes were prepared by a hydrothermal synthesis method,and then were used as carriers to react with 3-mercaptopropyl trimethoxysilane. Subsequently,the above-prepared intermediate was oxidized with hydrogen peroxide to afford sulfonic acid-functionalized titanium dioxide nanotubes(TNTs-SO_3H). The obtained TNTs-SO_3H was characterized by XRD,FTIR,TEM,TG and Hammett analysis techniques. The catalytic performance of TNTs-SO3H was investigated by esterification reaction of levulinic acid with n-butyl alcohol. The experiment results revealed that the TNTs-SO_3H catalyst exhibited high catalytic activity,and the yield of n-butyl levulinate reached 86. 5%under the following conditions: n(levulinic acid) ∶ n(n-butyl alcohol) = 1∶5,dosage of catalyst was 10%(based on mass of levulinic acid),at 120 ℃ for 4 h. In addition,the yield of target product still reached 81. 2% even if the catalyst was recycled for 7 times.
Titanium oxide nanotubes were prepared by a hydrothermal synthesis method,and then were used as carriers to react with 3-mercaptopropyl trimethoxysilane. Subsequently,the above-prepared intermediate was oxidized with hydrogen peroxide to afford sulfonic acid-functionalized titanium dioxide nanotubes(TNTs-SO_3H). The obtained TNTs-SO_3H was characterized by XRD,FTIR,TEM,TG and Hammett analysis techniques. The catalytic performance of TNTs-SO3H was investigated by esterification reaction of levulinic acid with n-butyl alcohol. The experiment results revealed that the TNTs-SO_3H catalyst exhibited high catalytic activity,and the yield of n-butyl levulinate reached 86. 5%under the following conditions: n(levulinic acid) ∶ n(n-butyl alcohol) = 1∶5,dosage of catalyst was 10%(based on mass of levulinic acid),at 120 ℃ for 4 h. In addition,the yield of target product still reached 81. 2% even if the catalyst was recycled for 7 times.
引文
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[3]Pileidis F D,Titirici M M.Production of liquid hydrocarbon fuels by catalytic conversion of biomass-derived levulinic acid[J].Chemsus Chem,2016,9(6):562-582.
[4]Murat Sen S,Gurbuz E I,Wettstein S G,et al.Production of butane oligomers as transportation fuels using butane for esterification of levulinic acid from lignocellulosic biomass:process synthesis and technoeconomic evaluation[J].Green Chem,2012,14(12):3289-3294.
[5]Bart H J,Reidetschlager J,Schatka K,et al.Kinetics of esterification of levulinic acid with n-butanol by homogeneous catalysis[J].Ind Eng Chem Res,1994,33(1):21-25.
[6]Su F,Wu Q,Song D,et al.Pore morphology-controlled preparation of Zr O2-based hybrid catalysts functionalized by both organosilica moieties and Keggin-type heteropoly acid for the synthesis of levulinate esters[J].J Mater Chem A,2013,1(2):13209-13221.
[7]Maheria K C,Kozinski J,Dalai A.Esterification of levulinic acid to n-butyl levulinate over various acidic zeolites[J].Catal Lett,2013,143(11):1220-1225.
[8]Melero J A,Morales G,Iglesias J,et al.Efficient conversion of levulinic acid into alkyl levulinates catalyzed by sulfonic mesostructured silicas[J].Appl Catal A:Gen,2013,466:116-122.
[9]Guo J J,Jin T S,Zhang S L,et al.Ti O2/SO2-4:an efficient and convenient catalyst for preparation of aromatic oximes[J].Green Chem,2001,3(4):193-195.
[10]Zhan Yongfu(战永复),Zhan Ruirui(战瑞瑞).Studies on SO2-4/Ti O2nano solid superacid systems[J].Chinese Journal of Inorganic Chemistry(无机化学学报),2002,18(5):505-508.
[11]Samantaray S K,Mishra T,Parida K M,et al.Studies on anion promoted Titania:2:Preparation,characterisation and catalytic activity towards aromatic alkylation over sulfated titania[J].J Mol Catal A:Chem,2000,156(1/2):267-274.
[12]Ryoo H I,Hong L Y,Jung S H,et al.Direct syntheses of sulfonated mesoporous Si O2-Ti O2-SO3H materials as solid acid catalysts[J].J Mater Chem,2010,20(31),6419-6421.
[13]Atghia S V,Beigbaghlou S S.Nanocrystalline titania-based sulfonic acid(Ti O2-Pr-SO3H)as a new,highly efficient,and recyclable solid acid catalyst for preparation of quinoxaline derivatives[J].J Nanostruct Chem,2013,3(1):38.
[14]Rahmani S,Amoozadeh A,Kolvari E.Nano titania-supported sulfonic acid:An efficient and reusable catalyst for a range of organic reactions under solvent free conditions[J].Catal Commun,2014,56:184-188.
[15]Kasuga T,Hiramatsu M,Hoson A,et al.Titania nanotubes prepared by chemical processing[J].Adv Mater,1999,11(15):1307-1311.
[16]Bavykin D V,Parmon V N,Lapkin A A,et al.The effect of hydrothermal conditions on the mesoporous structure of Ti O2nanotubes[J].J Mater Chem,2004,14,3370-3377.
[17]Atghia S V,Beigbaghlou S S.Nanocrystalline titania based sulfonic acid(Ti O2-Pr-SO3H)as a new,highly efficient and recyclable solid acid catalyst for the N-Boc protection of amines at room temperature[J].J Organomet Chem,2013,745-746:42-49.
[18]Nandiwale K Y,Niphadkar P S,Deshpande S S,et al.Esterication of renewable levulinic acid to ethyl levulinate biodiesel catalyzed by highly active and reusable desilicated H-ZSM-5[J].J Chem Technol Biotechnol,2014,89(10):1507-1515.
[19]Zhou X,Li Z X,Zhang C,et al.Efficient conversion of renewable levulinic acid to n-butyl levulinate catalyzed by ammonium and silver co-doped phosphotungstic acid[J].J Mol Catal A:Chem,2016,417:71-75.
[20]Melero J A,van Grieken R,Morales G.Advances in the synthesis and catalytic applications of organosulfonic-functionalized mesostructured materials[J].Chem Rev,2006,106(9):3790-3812.