SiO_2固化SO_3H-功能化离子液体催化合成油酸甲酯
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摘要
以1,3-丙烷磺内酯和巯基改性纳米二氧化硅球为原料,采用化学键合接枝法获得固化SO_3H-功能化离子液体的酸催化材料(SiO_2-IL)。采用NMR、FTIR和热分析方法对SiO_2-IL的结构和热稳定性进行了表征。考察了SiO_2-IL在油酸与甲醇酯化反应中的催化活性,分析了影响其催化性能的关键因素及原因。结果表明,该离子液体自身所具有的酸性以及固化过程中化学键合接枝程度均对其催化性能有所影响。对反应工艺条件进行了优化。结果表明,在反应温度60℃、n(甲醇)∶n(油酸)=12∶1、m(SiO_2-IL)∶m(油酸)=0.09∶1.00、反应时间5 h条件下,油酸甲酯收率最高为94%,催化材料经重复使用5次后,油酸甲酯收率仍可达74%。
A silica-immobilized SO_3H-functionalized ionic liquid( SiO_2-IL) was successfully synthesized via chemical bonding grafting method using 1,3-propane sultone and thiohydroxy modified nano-silica as raw materials. The structure and thermal stability of SiO_2-IL were characterized by NMR,FTIR and TGA. The catalytic activity of SiO_2-IL was evaluated for esterification of methanol with oleic acid,and the reason and some key factors affecting the catalytic performance were discussed. The results showed that the acidity of SO_3H-functionalized ionic liquid and the stability of chemical bonding grafting could affect the catalytic performance of SiO_2-IL. Moreover,the effects of reaction temperature,reaction time,molar ratio of reactants and the catalyst amount on the yield of methyl oleate were investigated. The results showed that under the optimal reaction conditions identi? ed( temperature 60℃ methanol to oleic acid molar ratio 12∶1,reaction time 5 h,mass ratio of SiO_2-ILto oleic acid 0. 09∶1. 00) the methyl oleate yield of 94% was obtained. After SiO_2-IL was reused for five times,the yield of methyl oleate could still reach 74%.
A silica-immobilized SO_3H-functionalized ionic liquid( SiO_2-IL) was successfully synthesized via chemical bonding grafting method using 1,3-propane sultone and thiohydroxy modified nano-silica as raw materials. The structure and thermal stability of SiO_2-IL were characterized by NMR,FTIR and TGA. The catalytic activity of SiO_2-IL was evaluated for esterification of methanol with oleic acid,and the reason and some key factors affecting the catalytic performance were discussed. The results showed that the acidity of SO_3H-functionalized ionic liquid and the stability of chemical bonding grafting could affect the catalytic performance of SiO_2-IL. Moreover,the effects of reaction temperature,reaction time,molar ratio of reactants and the catalyst amount on the yield of methyl oleate were investigated. The results showed that under the optimal reaction conditions identi? ed( temperature 60℃ methanol to oleic acid molar ratio 12∶1,reaction time 5 h,mass ratio of SiO_2-ILto oleic acid 0. 09∶1. 00) the methyl oleate yield of 94% was obtained. After SiO_2-IL was reused for five times,the yield of methyl oleate could still reach 74%.
引文
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[23]Zhang Jishen(张继申),Wan Hui(万辉),Guan Guofeng(管国锋).Preparation and catalytic performance of silica gel immobilized acidic ionic liquid catalyst[J].Chemical Reaction Engineering and Technology(化学反应工程与工艺),2008,24(6):503-508.
[24]Qiao K,Hagiwara H,Yokoyama C.Acidic ionic liquid modified silica gel as novel solid catalysts for esterification and nitration reactions[J].Journal of Molecular Catalysis A:Chemical,2006,246(1):65-69.
[25]Standardization Administration of the People's Republic of China(中国国家标准化管理委员会).Animal and vegetable fats and oils—determination of acid value and acidity(动植物油脂酸值和酸度测定):GB/T 5530-2005,[S].Bei Jing(北京):China National Institute of Standardization(中国标准化出版社),2005:8.
[26]Bo Yang(柏样),Man Ruilin(满瑞林),Xiao Guoguang(肖国光).Cxatlytic activities of acidic ionic liquids in synthesis of methyl oleate[J].Speciality Petrochemicals(精细石油化工),2010,27(3):56-60.
[27]Zhang Xuehong(张雪红),Gao Yanlei(高岩磊),Chen Rufen(陈汝芬),et al.Grafted imidazolium ionic liquid catalysts for synthesis of propylene carbonate[J].Natural Gas Chemical Industry(天然气化工),2013,38(1):15-19.
[28]Cai Yuan(蔡源),Huang Deying(黄德英),Wan Hui(万辉),et al.Preparation of a silica gel confined ionic liquid and its use as catalyst for esterification[J].Fine Chemicals(精细化工),2007,24(12):1196-1199.
[2]Avhad M R,Marchetti J M.A review on recent advancement in catalytic materials for biodiesel production[J].Renewable and Sustainable Energy Reviews,2015,50:696-718.
[3]Mohamad M,Ngadi N,Yahya N Y,et al.Prediction of biodiesel yield during trans-esterification process using response surface methodology[J].Fuel,2017,190:104-112.
[4]Berchmans H J,Hirata S.Biodiesel production from crude jatropha curcas l.seed oil with a high content of free fatty acids[J].Bioresource Technology,2008,99,1716-1721.
[5]Yu Hewei,Niu Shengli,Yang Yanzhao,et al.Preparation and esterification performance of sulfonated coal-based heterogeneous acid catalyst for methyl oleate production[J].Energy Conversion and Management,2016,128:488-496.
[6]Sun Yue(孙悦),Liang Lei(梁蕾),Ren Tieqiang(任铁强).Synthesis of oleic acid methyl oleate catalyzed by acidic ionic liquid[Hmim]HSO4[J].China Oils and Fats(油脂化工),2015,40(2):68-71.
[7]Throat T S,Yadav V M,Yadav G D.Esterification phthalicanhydride with 2-ethylhexnol by solid superacidic catalysts[J].Applied Catalysis,1992,90:73-76.
[8]Alpana P,Uma C.Metal(Ⅳ)tungstates as solid acid catalysts for the synthesis of phthalate diester-dioctyl phthalate(DOP)[J].Indian Journal of Chemical Technology,2003,10(1):44-47.
[9]Song Daiyu,An Sai,Guo Yihang,et al.Efficient conversion of levulinic acid or furfuryl alcohol into alkyl levulinates catalyzed by heteropoly acid and Zr O2bifunctionalized organosilica nanotubes[J].Journal of Catalysis,2016,333:184-199.
[10]Tao D J,Wu J,Wang Z Z,et al.SO3H-functionalized br8nsted acidic ionic liquids as efficient catalysts for the synthesis of isoamyl salicylate[J].Rsc Advances,2014,4(1):1-7.
[11]Han M H,Yi W L,Wu Q,et al.Preparation of biodiesel from waste oils catalyzed by a br8nsted acidic ionic liquid[J].Bioresource Technology,2009,100:2308-2310.
[12]Singh S K,Dhepe P L.Ionic liquids catalyzed lignin liquefaction:mechanistic studies using TPO-MS,FT-IR,Raman and 1D,2DHSQC/NOSEY NMR[J].Green Chemistry,2016,18:4098-4108.
[13]Han X X,He Y F,Hung C T,et al.Process optimization by response surface methodology and kinetic modeling for synthesis of methyl oleate biodiesel over H3PW12O40anchored montmorillonite K-10[J].Chemical Engineering Science,2013,104:64-72.
[14]Liang X Z,Yang J G.Synthesis of a novel multi-SO3H functionalized ionic liquid and its catalytic activities for biodiesel synthesis[J].Green Chemistry,2010,12,201-204.
[15]Ahmad H,Mohammad F,Nor A S A.Optimization of oleic-acid esterification catalyzed by ionic liquid for green biodiesel synthesis[J].Energy Conversion and Management,2013,76,818-827.
[16]Karimi B,Vafaeezadeh M.SBA-15-Functionalized sulfonic acid confined acidic ionic liquid:A powerful and water-tolerant catalyst for solvent-free esterifications[J].Chemical Communications,2012,48(27):3327-3329.
[17]Miao J,Wan H,Shao Y,et al.Acetalization of carbonyl compounds catalyzed by acidic ionic liquid immobilized on silica gel[J].Journal of Molecular Catalysis A:Chemical,2011,348(1/2):77-82.
[18]Rashinkar G,Kamble S,Kumbhar A,et al.An expeditious synthesis of homoallylic alcohols using br8nsted acidic supported ionic liquid phase catalyst with pendant ferrocenyl group[J].Catalysis Communications,2011,12:1442-1447.
[19]Karimi B,Elhamifar D,Clark J H,et al.Ordered mesoporous organosilica with ionic-liquid framework:an efficient and reusable support for the palladium-catalyzed Suzuki-Miyaura coupling reaction in water[J].Chemistry-A European Journal,2010,16:8047-8053.
[20]Cole A C,Jensecn J L,Ntai I,et al.Novel br8nsted acidic ionic liquids and their use as dual solvent-catalysts[J].Journal of the American Chemical Society,2002,124(21):5962-5963.
[21]Wang W J,Shao L L,Cheng W P,et al.Br8nsted acidic ionic liquids as novel catalysts for prins reaction[J].Catalysis Communications,2008,9(3):337-341.
[22]Valkenberg M H,Decastro C,Holderich W F.Immobilization of ionic liquids on solid supports[J].Green Chemistry,2002,4(2):88-93.
[23]Zhang Jishen(张继申),Wan Hui(万辉),Guan Guofeng(管国锋).Preparation and catalytic performance of silica gel immobilized acidic ionic liquid catalyst[J].Chemical Reaction Engineering and Technology(化学反应工程与工艺),2008,24(6):503-508.
[24]Qiao K,Hagiwara H,Yokoyama C.Acidic ionic liquid modified silica gel as novel solid catalysts for esterification and nitration reactions[J].Journal of Molecular Catalysis A:Chemical,2006,246(1):65-69.
[25]Standardization Administration of the People's Republic of China(中国国家标准化管理委员会).Animal and vegetable fats and oils—determination of acid value and acidity(动植物油脂酸值和酸度测定):GB/T 5530-2005,[S].Bei Jing(北京):China National Institute of Standardization(中国标准化出版社),2005:8.
[26]Bo Yang(柏样),Man Ruilin(满瑞林),Xiao Guoguang(肖国光).Cxatlytic activities of acidic ionic liquids in synthesis of methyl oleate[J].Speciality Petrochemicals(精细石油化工),2010,27(3):56-60.
[27]Zhang Xuehong(张雪红),Gao Yanlei(高岩磊),Chen Rufen(陈汝芬),et al.Grafted imidazolium ionic liquid catalysts for synthesis of propylene carbonate[J].Natural Gas Chemical Industry(天然气化工),2013,38(1):15-19.
[28]Cai Yuan(蔡源),Huang Deying(黄德英),Wan Hui(万辉),et al.Preparation of a silica gel confined ionic liquid and its use as catalyst for esterification[J].Fine Chemicals(精细化工),2007,24(12):1196-1199.