从粗羊毛脂中提取胆甾醇的工艺研究
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摘要
研究了以粗羊毛脂为原料提取胆甾醇的工艺过程,重点研究了从羊毛脂醇中提取胆甾醇的工艺过程。将原来的一次皂化过程改为二次皂化过程;将配合试剂由原来的六水氯化钙改为含40%水的氯化钙;将原来的直接在乙醇中配合,改为先用石油醚和水对羊毛脂醇进行萃取除杂,接着使羊毛脂醇在石油醚和少量乙醇中配合。通过研究,得出了各相关因素对胆甾醇纯度及收率的影响规律和相应的适宜工艺条件。
得出的适宜工艺条件如下:
对于羊毛脂皂化过程,第一次皂化碱用量为1.8倍理论碱量,时间为8h;第二次皂化碱用量也为1.8倍理论碱量,时间为6h。
对于皂化产物分离过程,氯化钙用量为理论用量的1.3倍,反应温度为25℃左右;对羊毛脂醇的萃取过程,第一次萃取,乙醇:粗羊毛脂(v:w)=4:1,萃取30min;第二次萃取,乙醇:粗羊毛脂(v:w)=2:1,萃取20min;第二次皂化转化只需一次萃取,乙醇:粗羊毛脂(v:w)=1.5:1,萃取20min。
对于胆甾醇的配合及其配合物提纯过程,萃取除杂时,石油醚:水:粗羊毛脂(v:w:w)=3:2:1;配合时,氯化钙:胆甾醇(mol:mol)=6:1,其中水:氯化钙(w:w)=2:3,配合温度为77~78℃,配合反应时间1h;提纯时,乙醇:石油醚(v:v)=3:50,降温速度为10℃/h,最终冷却温度为10℃。
对于配合物水解过程,水:粗羊毛脂(w:w)=10:1,温度为15℃左右,时间为1h。
对于胆甾醇的精制过程,乙醇:粗胆甾醇(v:w)=6:1,最终冷却温度为5℃。在上述适宜工艺条件下,得到的羊毛脂醇皂化值约为10mg/g,所得胆甾醇产品的纯度达90%以上,总收率可望达到60%以上,其质量基本符合美国
In the paper, the process of extraction of cholesterol from crude lanolin was studied, and the one from lanolin alcohol which is one of saponification production of lanolin were focused on. The once saponification was changed to the twain saponification. Change of complexing reagent from CaCl2·6H2O to hydrated CaCl2 with 40% water, and change of complexing solvent from ethanol to petroleum ether and a little ethanol were done, and the impurity in lanolin alcohol was extracted by petroleum ether and water before the complexing, so that the adduct yield was improved. On the base of study, the effects of every correlative factor on yield and purity of cholesterol, and the suited process conditions were presented.
The suited conditions of process were determined as follows:
For the process of crude lanolin saponification,NaOH dosage is 1.8 times to theoretic dosage, and reaction time is 8h in the first saponification, and NaOH dosage is the same multiple to first saponification, and the time is 6h in the second saponification.
For the separation of saponification results, CaCl2 dosage is 1.3 times to theretical dosage, and reaction temperature is 25℃. For the extractions of lanolin alcohol from calcium lanolin acid, the ratio of ethanol to lanolin is 4:1, 2:1 and 1.5:1 respectively, and the extraction time is 30min, 20min and 20min respectively.
For the complexing of cholesterol and purification of adduct, the ratio of petroleum ether to water and crude lanolin is 3:2:1 in the of romoving impurity, and the rate of CaCl2 to cholesterol is 6 by molecule, the rate of CaCl2 to water is 1.5
得出的适宜工艺条件如下:
对于羊毛脂皂化过程,第一次皂化碱用量为1.8倍理论碱量,时间为8h;第二次皂化碱用量也为1.8倍理论碱量,时间为6h。
对于皂化产物分离过程,氯化钙用量为理论用量的1.3倍,反应温度为25℃左右;对羊毛脂醇的萃取过程,第一次萃取,乙醇:粗羊毛脂(v:w)=4:1,萃取30min;第二次萃取,乙醇:粗羊毛脂(v:w)=2:1,萃取20min;第二次皂化转化只需一次萃取,乙醇:粗羊毛脂(v:w)=1.5:1,萃取20min。
对于胆甾醇的配合及其配合物提纯过程,萃取除杂时,石油醚:水:粗羊毛脂(v:w:w)=3:2:1;配合时,氯化钙:胆甾醇(mol:mol)=6:1,其中水:氯化钙(w:w)=2:3,配合温度为77~78℃,配合反应时间1h;提纯时,乙醇:石油醚(v:v)=3:50,降温速度为10℃/h,最终冷却温度为10℃。
对于配合物水解过程,水:粗羊毛脂(w:w)=10:1,温度为15℃左右,时间为1h。
对于胆甾醇的精制过程,乙醇:粗胆甾醇(v:w)=6:1,最终冷却温度为5℃。在上述适宜工艺条件下,得到的羊毛脂醇皂化值约为10mg/g,所得胆甾醇产品的纯度达90%以上,总收率可望达到60%以上,其质量基本符合美国
In the paper, the process of extraction of cholesterol from crude lanolin was studied, and the one from lanolin alcohol which is one of saponification production of lanolin were focused on. The once saponification was changed to the twain saponification. Change of complexing reagent from CaCl2·6H2O to hydrated CaCl2 with 40% water, and change of complexing solvent from ethanol to petroleum ether and a little ethanol were done, and the impurity in lanolin alcohol was extracted by petroleum ether and water before the complexing, so that the adduct yield was improved. On the base of study, the effects of every correlative factor on yield and purity of cholesterol, and the suited process conditions were presented.
The suited conditions of process were determined as follows:
For the process of crude lanolin saponification,NaOH dosage is 1.8 times to theoretic dosage, and reaction time is 8h in the first saponification, and NaOH dosage is the same multiple to first saponification, and the time is 6h in the second saponification.
For the separation of saponification results, CaCl2 dosage is 1.3 times to theretical dosage, and reaction temperature is 25℃. For the extractions of lanolin alcohol from calcium lanolin acid, the ratio of ethanol to lanolin is 4:1, 2:1 and 1.5:1 respectively, and the extraction time is 30min, 20min and 20min respectively.
For the complexing of cholesterol and purification of adduct, the ratio of petroleum ether to water and crude lanolin is 3:2:1 in the of romoving impurity, and the rate of CaCl2 to cholesterol is 6 by molecule, the rate of CaCl2 to water is 1.5
引文
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[2] 沈一丁,李小瑞,任庆海. 改性羊毛脂加脂剂的制备及性能. 精细化工,1996,13(2):12~15.
[3] 刘莉莉. 羊毛脂及其衍生物. 四川日化,1994,(1):52~54.
[4] Resheda Hagen,Oak Ridge. Lanolin/lanolin acid ester skin treatment composition. US 5,641,809,1997.
[5] 李国虎. 洗毛废水中提取纯净羊毛脂的新工艺. 上海环境科学,1996,15(9):28~29.
[6] 裘炳毅. 化妆品化学与工艺技术大全(上册). 北京:中国轻工业出版社,1997:54~64.
[7] 肖子英. 实用化妆品学. 天津:天津大学出版社,1999:17~18.
[8] 郑顺姬,强西怀,章川波. 羊毛脂的回收与精制. 皮革化工,2003,4(1):5~9.
[9] 王建新. 天然活性化妆品. 北京:中国轻工业出版社,1997:303.
[10] 张志贤. 油脂蜡检验. 上海科技卫生出版社, 1959:34.
[11] 陈小利,林苗,胡杰等. 进一步开发羊毛脂. 化学世界,2000,(1):8~12.
[12] 崔杨棣. 油脂中甾醇资源开发及其在甾体药物工业中的应用. 粮食与油脂,1997,4(40):25~31.
[13] 徐任生. 天然产物化学. 北京:科学出版社,1997:894.
[14] 林吉文. 甾体化学基础. 北京:化学工业出版社,1989:108.
[15] 《精细化工信息》编辑部. 美国化工产品及厂商名录大全. 南京:江苏省化工研究所,1994:536~537,971.
[16] Dead Sea Periclase. Parchem offers a broad range of lanolin products http://www.par-chem.com/,1998.
[17] 化工部情报所. 世界精细化工手册. 北京:化学工业部科学技术情报研究所,1982:477.
[18] Mr. Hasmukh N. Zaveri. Rolex Chemicals http://www.rolexanolin.com/,2004.
[19] NK Chemicals http://www.nkchemicals.com.sg/,2004.
[20] Lanolin Trading Co. Ltd. http://www.woolgrease.co.nz/,2004.
[21] 高燕生,鲁军成. 一种粗羊毛脂的精制工艺. CN:87100677A,1987.
[22] 韩才兴,倪家宝,赵何为等. 羊毛脂乙酰化反应研究. 日用化学工业,1987,(4):14~17. [23 ]陈孝忠,彭汉涛. 年产 250 吨羊毛脂聚氧乙烯衍生物的开发. 日用化学工业,1994,(1):14~17.
[24] 特奥·弗莱克恩斯坦,乔奇姆·波尔格尔德·格贝尔,弗兰茨·约瑟夫·卡达克. 由羊毛脂催化加氢制成羊毛脂醇的方法. CN:1039439A,1990.
[25] 田世光. 年产 100 吨羊毛脂衍生物 LAD-01 中试装置. 日用化学工业,1989,(5):18~22.
[26] Yamauchi, Yoshihito. Cholesterol recovery from wool grease by cultivating Aspergillus. Japan. Kokai 73 01,184, 1973.
[27] Yamauchi, Yoshihito. Separating cholesterol from wool wax. Japan. 73 03,393, 1973.
[28] 张根旺. 油脂化学. 北京:中国财政经济出版社,1999:132.
[29] Kohji Iuchi, Katsunci Dezawa. Wool alcohols and fatty acids. JP 76 139,806, 1976.
[30] Hisakazu Senda, Toshiaki Yamamoto, Hiroshi Ueno et al. Separation of wool fatty acid. US 3,983,147, 1976.
[31] Vladimir Schuarz, Pavel Pihera. Separation of lanolin alcohol fraction from hydrolyzed lanolin. CS 237,195, 1987.
[32] 毛法根,郑筱凤. 从羊毛脂中制取羊毛酸两价金属皂. CN 86,100,362 A, 1987.
[33] 张珏,华聘聘. 羊毛脂皂化工艺的研究. 中国油脂,2000,25(2):64~67.
[34] Brian Robinson, Ali Safdar, Rober Step Davidson. Saponification of fats and oils. GB 2,170,507, 1985.
[35] 朱晓康. 羊毛脂的回收及其改性产品. 精细化工信息,1991,(10):1~5.
[36] 章思规. 精细有机化学品手册. 北京:科学出版社,1991:521~522.
[37] 欧阳平凯. 化工产品手册. 第三版·生物化工产品. 北京:化学工业出版社,1999:290.
[38] Amerchol P. Edison. Wool wax alcohols: A Review. Journal of the American Oil Chemists Society, 1979, 56(6): 651～658.
[39] E. V. Truter. The extraction of cholesterol from wool wax alcohols. Manufacturing Chemist. 1955, 26: 231~5.
[40] Van Dam, Mathieu Jan Daniel, De Lange, Harrie Reinder, et al. Method of isolating sterols in commercial quantities from sterol-containing material. EP 53,415, 1982.
[41] Timothy J. Barder, W. Brian Bedwell, Steven P. Johnson. Separation of sterols from low-acid feeds with magnesium silicate and methyl-tert-butyl ether desorbent. US 4,977,243, 1990.
[42] Katsunci Ohnishi, Koji Iuchi, Tadao Teramoto. Treatment of waste water from scouring of wool. Japan. Kokai 74 120,454, 1974.
[43] Jan Guengros, Juraj Lutisan. Process for preparing sterol alcohols from lanolin. CZ 279,996, 1995.
[44] 石井穆,川口享子. ウールグリース成分の分離法. 昭 53-61604,1978.
[45] Zh. S. Sydykov, A. P. Yavkin, G. M. Segal et al. Indentification of some wool wax components. Khim-Farm Zh, 1978, 12(1): 138~142.
[46] Colin Leslie Hewett. Process for isolation of cholesterol from wool wax alcohols. Brit. 646,227, 1950.
[47] Colin Leslie Hewett. Isolation of cholesterol from wool alcohols. Brit. 690,879, 1953.
[48] Kohji Iuchi, Katsumi Dezawa. Separation and purification of cholesten-3β-ol. JP 76 70,800, 1976.
[49] Charles H. Foster. Process for separating 3-hydroxy steroids or sterols from mixtures such as lipids. US 4,279,828, 1981.
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