研磨强化无溶剂法合成蔗糖脂肪酸酯
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摘要
以蔗糖和脂肪酸甲酯为反应原料,无溶剂条件下采用研磨强化的方法合成了蔗糖脂肪酸酯(即蔗糖酯),考察了研磨时间、乳化剂用量、反应时间、反应压力以及催化剂用量对蔗糖酯收率及脂肪酸甲酯转化率的影响,产品经水洗、醇提精制后,用FTIR和HPLC-ELSD对其进行了表征和分析。结果表明:研磨处理能将反应分散物粒径(D50)降至约5μm,有效地增强了蔗糖与脂肪酸甲酯的无溶剂酯交换反应。得到的最优反应条件为:研磨时间为60min,硬脂酸钾乳化剂质量分数为10%(占体系总质量,下同),K2CO3质量分数为2.0%,反应时间6 h,反应压力0.5 kPa,在该条件下脂肪酸甲酯转化率为91.2%,蔗糖酯收率为61.6%。精制后产品中蔗糖酯质量分数为81.9%,且其游离糖质量分数为0.6%,酸值为3.0mgKOH/g,水分(质量分数)为0.2%和灰分(质量分数)为0.5%,均达到FAO/WHO标准。
A grind-strengthened strategy was developed for the solvent-free synthesis of sucrose fatty acid esters(SE).The effects of grinding time,emulsifier,reaction time,reaction pressure and catalyst dosage on the yields and production distributions of SE and the conversion of fatty acid methyl ester were investigated.After the generated SE was purified by using water washing and alcohol extraction,the obtained product was characterized by Fourier transform infrared spectroscopy(FTIR) and high performance liquid chromatography-evaporative light scattering detector(HPLC-ELSD).The results showed that the grinding pretreatment could reduce the particle size of reaction dispersion(D50) to 5 μm and effectively enhanced the solvent-free transesterification reaction of sucrose esters.Under the optimized conditions,a fatty acid methyl ester conversion of 91.2% and a SE yield of 61.6% were achieved,in which the grinding time was 60 min,the mass fraction of potassium stearate was 10%(based on the total mass of the system,the same below),the mass fraction of potassium carbonate was 2.0%,the reaction pressure was 0.5 kPa,and the reaction time was 6 h.After purification,the mass fraction of SE reached up to 81.9%,and its free sugar content was 0.6%(mass fraction),acid value was 3.0 mg KOH/g,water content was 0.2%(mass fraction),ash content was 0.5%(mass fraction).All these indicators completely accorded with the Food and Agriculture Organization/World Health Organization(FAO/WHO) standard.
A grind-strengthened strategy was developed for the solvent-free synthesis of sucrose fatty acid esters(SE).The effects of grinding time,emulsifier,reaction time,reaction pressure and catalyst dosage on the yields and production distributions of SE and the conversion of fatty acid methyl ester were investigated.After the generated SE was purified by using water washing and alcohol extraction,the obtained product was characterized by Fourier transform infrared spectroscopy(FTIR) and high performance liquid chromatography-evaporative light scattering detector(HPLC-ELSD).The results showed that the grinding pretreatment could reduce the particle size of reaction dispersion(D50) to 5 μm and effectively enhanced the solvent-free transesterification reaction of sucrose esters.Under the optimized conditions,a fatty acid methyl ester conversion of 91.2% and a SE yield of 61.6% were achieved,in which the grinding time was 60 min,the mass fraction of potassium stearate was 10%(based on the total mass of the system,the same below),the mass fraction of potassium carbonate was 2.0%,the reaction pressure was 0.5 kPa,and the reaction time was 6 h.After purification,the mass fraction of SE reached up to 81.9%,and its free sugar content was 0.6%(mass fraction),acid value was 3.0 mg KOH/g,water content was 0.2%(mass fraction),ash content was 0.5%(mass fraction).All these indicators completely accorded with the Food and Agriculture Organization/World Health Organization(FAO/WHO) standard.
引文
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[13]Mugunthan G,Ravindranathan Kartha K P.Application of ball milling technology to carbohydrate reactions-II:Solvent-free mechanochemical synthesis of glycosylazides[J].Journal of Carbohydrate Chemistry,2008,27(5):294-299.
[14]Li Kai(李凯),Meng Lidan(蒙丽丹),Su Jiating(苏佳廷),et al.Synthesis of sucrose laurate via transesterification underdualfrequency ultrasonic irradiation[J].Applied Chemical Industry(应用化工),2016,45(7):1224-1227.
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[16]People's Republic of China National Health and Family Planning Commission(中华人民共和国国家卫生和计划生育委员会).Food additivessucrose fatty acid ester(食品添加剂蔗糖脂肪酸酯):GB1886.27-2015[S].Beijing:China Standard Publishing House,2015:9-22.
[17]State General Administration of the People's Republic of China for Quality Supervision and Inspection andQuarantine(中华人民共和国国家质量监督检验检疫总局),China National Standardization Administration(中国国家标准化管理委员会).Determination of ignition residue for organic chemical products(有机化工产品灼烧残渣的测定):GB/T 7531-2008[S].Beijing:China Standard Publishing House,2008:6-4.
[2]Douglas K A,Bernard Y T.Carbohydrate-alkyl ester derivatives as biosurfactants[J].Journal of Surfactants and Detergents,1999,2(3):383-390.
[3]Ran Y,Douglas G H,Rachel B.Effects of particle size of sucrose suspensions and pre-incubation of enzymes on lipase-catalyzed synthesis of sucrose oleic acid esters[J].Journal of the American Oil Chemists’Society,2014,91(11):1891-1901.
[4]Lin X S,Zou Y,Zhao K H,et al.Tetraalkylammonium ionic liquids as dual solvents-catalysts for direct synthesis of sugar fatty acid esters[J].Journal of Surfactants and Detergents,2016,19(3):511-517.
[5]Tomone S,Yuto K,Naomi S K.Process design for green and selective production of bio-based surfactant with heterogeneous resin catalyst[J].Chemical Engineering Journal,2018,334:2231-2237.
[6]Zhang Yadong(章亚东),Gao Xiaolei(高晓蕾),Jiang Denggao(蒋登高),et al.Synthesis of sucrose ester with no-solvent method[J].Journal of Chemical Engineering of Chinese Universities(高校化学工程学报),2002,5(16):519-523.
[7]Fitremann J,Queneau Y,Maitre J P,et al.Co-melting of solid sucrose and multivalent cation soaps for solvent-free synthesis of sucrose esters[J].Tetrahedron Letters,2007,48(23):4111-4114.
[8]Tülay P,Robert J L.Syntheses and applications of sucrose-based esters[J].Journal of Surfactants and Detergents,2001,4(4):415-421.
[9]Wang Q H,Zhang S F,Yang J Z.Regioselective formation of6-O-acylsucroses and 6,3?-di-O-acylsucroses via the stannyleneacetalmethod[J].Carbohydrate Research,2007,342(17):2657-2663.
[10]Lu Y Y,Yan R,Ma X,et al.Synthesis and characterization of raffinose fatty acid monoesters under ultrasonic irradiation[J].European Food Research and Technology,2013,237(2):237-244.
[11]Li Zuyi(李祖义),Shi Yiping(施邑屏),Yuan Changgui(袁长贵).The synthesis of sucrose esters by homogeneous non-solvent method[J].Shanghai Chemical Industry(上海化工),1999,24(19):16-17.
[12]Peng Yangxi(彭秧锡),Chen Qiyuan(陈启元),Liu Shijun(刘士军),et al.Research status and prospect of mechanochemistry[J].Materials Science&Technology(材料科学与工艺),2009,17(1):113-117.
[13]Mugunthan G,Ravindranathan Kartha K P.Application of ball milling technology to carbohydrate reactions-II:Solvent-free mechanochemical synthesis of glycosylazides[J].Journal of Carbohydrate Chemistry,2008,27(5):294-299.
[14]Li Kai(李凯),Meng Lidan(蒙丽丹),Su Jiating(苏佳廷),et al.Synthesis of sucrose laurate via transesterification underdualfrequency ultrasonic irradiation[J].Applied Chemical Industry(应用化工),2016,45(7):1224-1227.
[15]The Joint FAO/WHO Expert Committee on Food Additives(JECFA):73rd JECFA(2010)FAO JECFA Monographs.Sucrose esters of fatty acids[S].Food and Agriculture Organization of the United Nations,2010:10.
[16]People's Republic of China National Health and Family Planning Commission(中华人民共和国国家卫生和计划生育委员会).Food additivessucrose fatty acid ester(食品添加剂蔗糖脂肪酸酯):GB1886.27-2015[S].Beijing:China Standard Publishing House,2015:9-22.
[17]State General Administration of the People's Republic of China for Quality Supervision and Inspection andQuarantine(中华人民共和国国家质量监督检验检疫总局),China National Standardization Administration(中国国家标准化管理委员会).Determination of ignition residue for organic chemical products(有机化工产品灼烧残渣的测定):GB/T 7531-2008[S].Beijing:China Standard Publishing House,2008:6-4.