过氧硼钨酸季铵盐催化光皮树油环氧化的研究
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摘要
自制过氧硼钨酸季铵盐催化剂,并在H_2O_2为氧化剂,乙酸乙酯为溶剂,无羧酸条件下催化光皮树油环氧化,考察了各反应条件对环氧化的影响。实验结果表明:10 g光皮树油(双键约49 mmol),在反应温度60℃,反应时间4 h,H_2O_2与油脂中双键物质的量比为1.2∶1.0,催化剂过氧硼钨酸季铵盐用量为0.1 g的条件下,产物达到最高环氧值4.52%,此时双键转化率为77.4%,环氧产物选择性为74.7%。
Peroxy quaternary ammonium borotungstate catalyst was prepared in this study. The synthesized catalyst was used in the epoxidation of Cornus wilsoniana Wangerin( wilson dogwood) oil using H_2O_2 as oxidant and ethyl acetate as solvent in the absence of carboxylic acid. The effects of reaction conditions on the epoxidation were studied. Under the optimum conditions of oil 10 g( double bond 49 mmol),reaction temperature 60 ℃,reaction time 4 h,H_2O_2 to double bond molar ratio 1. 2 ∶ 1. 0 and catalyst 0. 1 g,the product epoxy value was up to 4. 52%. Conversion and selectivity of double bond were 77. 4% and 74. 4%,respectively.
Peroxy quaternary ammonium borotungstate catalyst was prepared in this study. The synthesized catalyst was used in the epoxidation of Cornus wilsoniana Wangerin( wilson dogwood) oil using H_2O_2 as oxidant and ethyl acetate as solvent in the absence of carboxylic acid. The effects of reaction conditions on the epoxidation were studied. Under the optimum conditions of oil 10 g( double bond 49 mmol),reaction temperature 60 ℃,reaction time 4 h,H_2O_2 to double bond molar ratio 1. 2 ∶ 1. 0 and catalyst 0. 1 g,the product epoxy value was up to 4. 52%. Conversion and selectivity of double bond were 77. 4% and 74. 4%,respectively.
引文
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[16]胡红定,朱明乔,童张法,等.新型钨基催化剂上环己烯环氧化反应[J].化工学报,2015,66(8):3007-3013.HU Hong-ding,ZHU Ming-qiao,TONG Zhang-fa,et al.Novel tungsten-based catalyst for epoxidation of cyclohexene[J].CIESC Journal,2015,66(8):3007-3013.
[17]胡红定.硼钨杂多酸季铵盐催化环已烯双氧水环氧化研究[D].杭州:浙江大学硕士学位论文,2014.HU Hong-ding.Cyclohexene epoxidation using hydrogen peroxide as oxidant and quaternary ammonium heteropolytungstobotare as catalyst[D].Hangzhou:Master Degree Thesis of Zhejiang University,2014.
[2]史润萍,蒋平平,施赛泉.大豆酸化油甲酯环氧化合成无毒环保型增塑剂[J].中国油脂,2008,33(6):36-39.SHI Run-ping,JIANG Ping-ping,SHI Sai-quan.Epoxidized synthesis of nontoxic and environmental-friendly plasticizer from soy acidic oil methyl esters[J].China Oils and Fats,2008,33(6):36-39.
[3]SRIKNATA D,ANAND V P,VAIBHAV V G,et al.Epoxidation of cotton seed oil by aqueous hydrogen peroxide catalyzed by liquid inorganic acids[J].Bioresource Technology,2008,99(9):3737-3744.
[4]聂小安,蒋剑春,陈水根,等.环氧脂肪酸甲酯的合成及其降凝性能初探[J].林产业化学与工业,2008,28(2):48-52.NIE Xiao-an,JIANG Jian-chun,CHEN Shui-gen,et al.Synthesis of epoxy fatty acid methylesters and preliminary exploration on their pour-point depressing properties[J].Chemistry and Industry of Forest Products,2008,28(2):48-52.
[5]孙晓英,赵雪冰,杜伟.微量硫酸催化环氧大豆油的合成[J].过程工程学报,2010,10(4):714-719.SUN Xiao-ying,ZHAO Xue-bing,DU Wei.Preparation of epoxidized soybean oil by catalysis of small amount of sulfuric acid[J].The Chinese Journal of Process Engineering,2010,10(4):714-719.
[6]曹玮,马新启,曲波,等.环氧大豆油新工艺的研究[J].化工时刊,2002,16(2):49-51.CAO Wei,MA Xing-qi,QU Bo,et al.A research on new methodology of epoxy soybean oil[J].Chemical Industry Times,2002,16(2):49-51.
[7]FISER S S,JANKOVIC M,PETROVIC Z S.Kinetics of in situ epoxidation of soybean oil in bulk catalyzed by ion exchange resin[J].Journal of the American Oil Chemistis'Society,2001,78(7):725-731.
[8]KAMATA K,YONEHARA K,SUMIDA Y,et al.Efficient epoxidation of olefins with≥99﹪selectivity and use of hydrogen peroxide[J].Science,2003(300):964-966.
[9]RIOS L A,WECKES P,SCHUSTER H.Mesoporous and amorphous Ti-silicas on the epoxidation of vegetable oil[J].Journal of Catalysis,2005,232(1):19-26.
[10]陈旻,蒋平平,叶夏,等.生物油脂新型环氧化过程及机理研究[J].化学学报,2009,67(13):1412-1416.CHEN Min,JIANG Ping-ping,YE Xia,et al.New epoxidation process of biological oils and fats and its mechanism[J].Acta Chimica Sinica,2009,67(13):1412-1416.
[11]MOHAMMED L,DOMINIQUE A,AHMED B,et al.Solvent-free epoxidation of himachalenes and their derivatives by TBHP using[Mo O2(SAP)]2as a catalyst[J].Comptes Rendus Chimie,2014,17(6):549-556.
[12]刘元法,王兴国,员克志.脂肪酶催化制备环氧棉籽油的研究[J].中国油脂,2007,32(1):39-42.LIU Yuan-fa,WANG Xing-guo,YUAN Ke-zhi.Preparation of epoxy cottonseed oil catalyzed by lipase[J].China Oil and Fats,2007,32(1):39-42.
[13]VENTURELLO C,ALNERI E,RICCI M.A new,effective catalytic system for epoxidation of olefins by hydrogen peroxide under phase-transfer conditions[J].The Journal of Orgonic Chemistry,1983,48(21):3831-3833.
[14]POLI E,CLACENS J M,BARRAULT J,et al.Solvent-free selective epoxidation of fatty esters over a tungsten-based catalyst[J].Catalysis Today,2009,140(1/2):19-22.
[15]POLI E,BION N,BARRAULT J,et al.Selective epoxidation of unsaturated fatty esters over peroxophosphotungstic catalysts(POW)under solvent free conditions:Study of the POW catalyst's mechanism[J].Catalysis Today,2010,157(1/2/3/4):371-377.
[16]胡红定,朱明乔,童张法,等.新型钨基催化剂上环己烯环氧化反应[J].化工学报,2015,66(8):3007-3013.HU Hong-ding,ZHU Ming-qiao,TONG Zhang-fa,et al.Novel tungsten-based catalyst for epoxidation of cyclohexene[J].CIESC Journal,2015,66(8):3007-3013.
[17]胡红定.硼钨杂多酸季铵盐催化环已烯双氧水环氧化研究[D].杭州:浙江大学硕士学位论文,2014.HU Hong-ding.Cyclohexene epoxidation using hydrogen peroxide as oxidant and quaternary ammonium heteropolytungstobotare as catalyst[D].Hangzhou:Master Degree Thesis of Zhejiang University,2014.