臺灣博碩士論文加值系統

摘要

本實驗利用不同溶劑以0~-2.5℃之冬化試驗，尋找最佳溶劑及最佳固體脂與、液體油分離溫度之條件，並以融點作為研判羊毛脂分離效果之補助判斷。其中以丙酮為溶媒之冬化效果最佳，溫度設定在0℃即可充分達到分離效果；異丙醇與正己烷冬化溫度則分別下降至-20~-2.5℃始可分離出常溫為液體羊毛油（融點14-17℃）之品質；固體脂融點均為大於40 ℃。將液體羊毛油以活性白土或矽膠G 60在80 ℃加熱2小時精製後，均可達無獸臭腥味之清徹之品質。亦可利用活性白土或矽膠G 60管柱以非極性溶劑沖提非極性油脂，以極性溶劑沖提極性物質，亦可達到精製羊毛油之品質效果，利用羊毛脂來萃取膽固醇，以原羊毛脂及液體羊毛油在相同25 % 氫氧化鈉、80 ℃條件來皂化，發現以粗羊毛脂皂化後，收率少及處理過程較繁瑣，且藥品浪費較多等缺點；如以經冬化後液體油含15 % 膽固醇可提高28~30 %。再經皂化比以粗羊毛脂皂化之操作上，更容易得到羊毛醇及有效地縮短、皂化時間，羊毛醇中膽固醇可達40～45 %，再以此羊毛醇經冰醋酸及甲醇分離純化後，膽固醇純度可達90~95 %。

Abstract

The purpose of this experiment was looking for the best separating condition of wool grease with different solvents and temperature from 0~25℃. The result was revaluated by the melting point. At the temperature of 0℃ for acetone was showed the separation very well. The temperature as 10, as -20~-2.5℃ for isopropyl alcohol and hexane was used to separate the grease, into solid for and liquid oil. The melting point for both was higher than 40℃ and 14~17℃ respectively. The liquid oil was refined by activated clay or silica gel G60 at temperature of 80℃ for 2 hours. The product will be transparent without off flavors. In addition, the refined Lanoline oil also could be done by non-polar and polar solvent to extract the non-polar and polar grease wits the column of activated clay.
The cholesterol was extracted by the saporification of wool grease and liquid oil with 25％ NaOH at the temperature of 80℃. The result of wool grease was indicated the lower yield, much more complex processing procedure and more chemical agent wasted. However, the group of winter liquid oil was of the amount of cholesterol increased from
15％ to 28~30％. This product was saponified again ,the cholesterol was extracted watch easier, shorter period of time , higher yield of 40~45％ and better purity of 90~95% as well.

目錄

中文摘要----------------------------------------------------------------------------------- VI
英文摘要----------------------------------------------------------------------------------- VII
壹、前言-----------------------------------------------------------------------------------. 1
貳、文獻整理
一、羊毛脂之沿革----------------------------------------------------------------- 3
二、羊毛脂之萃取----------------------------------------------------------------- 4
三、Lanolin之性狀與構成成份---------------------------------------------- 4
四、Lanolin特性及應用--------------------------------------------------------- 14
五、羊毛脂的皂化----------------------------------------------------------------- 16
六、膽固醇對甲殼類的功能--------------------------------------------------- 17
七、油脂之冬化--------------------------------------------------------------------- 19
八、影響溶劑冬化之因素------------------------------------------------------ 20
九、液體Lanoline之精製------------------------------------------------------ 25
十、膽固醇之萃取精製--------------------------------------------------------- 26
參、 材料與方法
一、材料
(一)羊毛脂來源------------------------------------------------------------------- 27
(二)溶劑------------------------------------------------------------------------------ 27
(三)藥品------------------------------------------------------------------------------ 27
(四)標準品-------------------------------------------------------------------------- 27
(五)吸附劑-------------------------------------------------------------------------- 27


二、實驗方法
(一)羊毛脂冬化分別實驗----------------------------------------------------- 28
(二)羊毛液體油脫臭法與管柱混合式新精製法--------------------- 28
(三)羊毛脂皂化法--------------------------------------------------------------- 31
(四)膽固醇萃取與精製-------------------------------------------------------- 31
(五)酸價----------------------------------------------------------------------------- 34
(六)色澤測定---------------------------------------------------------------------- 35
(七)熔點測定--------------------------------------------------------------------------- 35
(八)紫外光掃描------------------------------------------------------------------- 35
(九)薄層色層分析---------------------------------------------------------------- 37
(十)膽固醇之測定--------------------------------------------------------------- 38
(十一)傅立葉紅外線轉換紅外線光譜之測定------------------------ 40
肆、結果與討論
一、羊毛廠生產羊毛品質與性狀------------------------------------------- 41
二、羊毛脂之冬化與固體酯、液體油分離之探討
(一)不同溶劑對羊毛脂在0℃冬化的影響---------------------------- 44
(二)不同溶劑在不同溫度下之冬化下，液體羊毛油分離效果 46
三、粗羊毛液體油的精製
(一)不同脫色劑之脫色效果
1.利用活性白土精製法------------------------------------------------------ 57
2.利用矽膠G 60精製法---------------------------------------------------- 57
3.利用管柱精製法------------------------------------------------------------- 60
四、粗羊毛脂之皂化與膽固醇萃取之探討
(一)粗羊毛脂在25 % 低鹼液之皂化------------------------------------- 65
(二)粗羊毛脂在高鹼液（50 ﹪）之皂化與膽固醇之萃取------- 67
五、液體羊毛油之皂化與膽固醇萃取之條件探討
(一)鹼濃度對液體羊毛油之皂化影響-------------------------------- 69
(二)液體羊毛油皂化作用中，對於產生皂化物與未皂化物中
膽固醇含率之變化---------------------------------------------------------

73
(三)在25 %NaOH濃度下，加熱溫度對羊毛液體油之皂化效果之影響--------------------------------------------------------------------------

75
六、羊毛脂與冬化後固體酯與液體油在完全皂化後之不皂化物中膽固醇含量之比較----------------------------------------

80
七、膽固醇之經外線光譜儀 (IR) 與紫外光掃描 (UV) 測定 82
伍、結論---------------------------------------------------------------------------------- 87
陸、參考文獻----------------------------------------------------------------------------- 88















表目錄

表一、羊毛脂之脂肪酸類組成（一）-------------------------------------- 6
表二、羊毛脂之脂肪酸組成（二）----------------------------------------- 7
表三、羊毛脂之醇類組成（一）-------------------------------------------- 9
表四、羊毛脂之醇類組成（二）--------------------------------------------- 10
表五、各種飽和與不飽和脂肪酸之融點及來源比較-------------------- 23

表六、溶劑洗毛之羊毛脂品質及性狀----------------------------------- 42
表七、A、B及C級羊毛脂之膽固醇含量--------------------------------- 43
表八、不同溶劑對羊毛脂在0℃冬化的效果----------------------------- 45
表九、羊毛脂利用丙酮、正己烷及異丙醇多段冬化之效果---------- 49
表十、羊毛脂利用丙酮多段冬化分離之效果----------------------------- 51
表十一、羊毛脂利用正己烷多段冬化分離之效果----------------------- 52
表十二、羊毛脂利用異丙醇多段冬化分離之效果------------------------ 54
表十三、不同脫色劑對液體羊毛油脫臭、脫色效果之------------------ 56
表十四、添加20%活性白土量與加熱時間對羊毛油品質之收率影響 58
表十五、添加20%矽膠G 60與加熱時間對羊毛油品質及收率影響 63
表十六、羊毛脂利用管柱分離極性與非極性油脂之精------------------ 76
表十七、羊毛脂之高鹼液（50 ％鹼液）皂化及膽固醇------------------ 78
圖目錄

圖一、膽固醇之結構式-------------------------------------------------------- 12
圖二、羊毛固醇之結構式----------------------------------------------------- 12
圖三、膽固醇酯之結構式----------------------------------------------------- 13
圖四、羊毛固醇酯之結構式-------------------------------------------------- 13
圖五、從粗羊毛脂分離固體酯及液體油之冬化流程-------------------- 29

圖六、羊毛液體油之管柱精製法流程-------------------------------------- 30
圖七、粗羊毛脂及冬化後羊毛固體脂及液體油之皂化流程----------- 32
圖八、液體油之膽固醇萃取與精製流程圖-------------------------------- 33
圖九、標準膽固醇羊毛固醇及硬酯酸之紫外光掃描圖----------------- 36
圖十、Zurkowski法膽固醇發色變化----------------------------------------- 39
圖十一、膽固醇濃度標準曲線圖-------------------------------------------- 66
圖十二、粗羊毛脂成分分析--------------------------------------------------- 63
圖十三、羊毛脂冬化後固體酯與液體油之TLC分析------------------ 64
圖十四、粗羊毛脂在25 % NaOH 、80℃下皂化時間與未皂化物
之TLC----------------------------------------------------------------
66
圖十五、液體羊毛油以25 % 鹼濃度 (對羊毛油)，於80℃下加熱皂
化時間之膽固醇酯其變化情形之薄層色層分析圖-----------

70
圖十六、液體羊毛油以20 % 鹼濃度 (對羊毛油)，於80℃下加熱皂化時間之膽固醇酯其變化情形之薄層色層------------------

71
圖十七、液體羊毛油以15 % 鹼濃度 (對羊毛油)，於80℃下加熱皂化時間之膽固醇酯其變化情形之薄層色層--------------------

72
圖十八、液體羊毛油以25 % 鹼液濃度及80 ℃加熱皂化中皂化物
與未皂化物中膽固醇含量之變化--------------------------------

74
圖十九、70℃溫度、在25% 鹼濃度對液體羊毛油的皂化影響------
76
圖二十、80℃溫度、在25% 鹼濃度對液體羊毛油的皂化影響-------
77
圖二十一、90℃溫度、在25 % 鹼濃度對液體羊毛油的皂化影響-- 78
圖二十二、以25 % 鹼濃度，在不同溫度對液體羊毛油皂化之影響 79
圖二十三、粗羊毛脂及冬化後固體酯及液體油在鹼濃度25 %、80 ℃完全皂化後不皂化物中膽固醇含量之比較------------------

81
圖二十四、標準品膽固醇及羊毛固醇之紅外線光譜分析圖----------- 83
圖二十五、由羊毛醇中分離之純化膽固醇及羊毛固醇之IR圖------- 84
圖二十六、純化之膽固醇紫外光掃描圖----------------------------------- 85
圖二十七、從A、B級羊毛脂皂化物中分離羊毛固醇之紫外光掃描 86

參考文獻

川口亨子，1978。羊毛脂分離方法。日本公開特許公報，昭56-36507。
毛法根、鄭荻風，1987。從羊毛脂中製取羊毛酸兩價金屬皂。中國專利86100362 A。
半山智、鈴木修武、飯村和夫、雲埼和雄、竹下安見兒、田中章夫、田邊智志、丹野裕之、山埼惠和中康，1991。總極性化合物定量。
吉川史朗，1980。工業雜誌期待。油脂，33（2）:42-46。
李政德、張壽昌、劉廷英，1981。棕櫚油之應用（1）棕櫚油之交互酯化及溶劑區分，食品工業發展研究報告第251號。
李政德、張壽昌，1982。棕櫚油之應用（2）以棕櫚油製造可可代用脂之研究，食品工業發展研究報告第286號。
吳光照、潘文智，1984。棕櫚油區分物的利用，食品工業發展研究報告第358號。
朱曉康，1991。羊毛脂的回收及其改性產品，精細化工資訊期刊，10: 1-5。
沈一丁、李小瑞、任慶海，1996。改性羊毛脂加脂劑的製備及性能，精細化工期刊，13（2）: 12～15。
油脂化學製品便覽編集委員會，1975。油脂化學製品便覽，278-289.
長穀部義範，1966。Wool grease and lanolins，Sansho oil Fat Co., LTD，1-3。
阿武喜美子、長穀川榮一，1972。多糖實驗法ㄙㄅ【1】，31-84，南江堂，日本京都。
岩永辛也，1977。介面活性劑用油脂分別，油化學，26: 683。
翁瑞光、孫璐西，1989影響油脂溶劑區分效果因素的探討，27: 218
野島莊北、冰井克孝，1969。薄層分析法。脂質(朝倉書局)，271-277。
陳錫秋、林慶永、羅淑華，1986。從羊毛脂中萃取膽固醇之工業生產之研究，利華羊毛研究報告(1)。1-10。
陳錫秋、羅淑華、林永慶，1987。從wool grease中分離lanoline oil之工業生產之研究，利華羊毛研究報告(2)。2-11。
陳錫秋，1990。羊毛固醇替代膽固醇應用於草蝦養殖之效果之研究，，利華羊毛研究報告(3)。1-10。
陳明汝、張瑞藍、群傑合著，2000。食品分析與檢驗，華格那企業。
曾名佑，1996。劣變油脂中極性物質導致老鼠肝脂肪變性之探討，碩士論文。15-17。
鄭順順、強西懷、張鴻飛、章川波，2002。羊毛脂及其衍生物在皮革化學品研究中的應用，日用化學工業期刊，第6期。
潭蘭蘭、楊景昌，2001。羊毛脂皂化及其皂物的分離，四川化工與腐蝕控制，4（5）: 14～19。
藤堂信義。1978。植物脂肪酸生產上的利用。油化學，27（10）: 667～668。
A.O.A.C. 1998.’’ Official Methods of Analysis’’, 16 edition, Association of official Analytical Chemists Maryland.
Amer, M. A., Kupranycz, D. B. and Baker, B. E. 1985. Physical and chemical characteristics of butterfat fractions obtained by crystallization from molten fat. Ibid. 62：1551.
Arul, J., Bordereau, A., Malhlouf, J., Trardif, R. and Grenier, B. 1988. Distribution of cholesterol in milk fractions. The Journal of Dairy Research 55：361.
Billek, G., Guhr, G. and Waibel, J. 1978. Quality assessment of used frying fat：A comparison of four methods. Journal of the American Oil Chemists' Society 55: 728.
Brian, R., Ali, S. and Rober, S. D. 1985. Saponification of fats and oils. Journal GB 2170507.
Bussey, D. M., Ryan, T. C., Gray, J. I. and Zabik, M. E. 1981. Fractionation and characterization of edible tallow. Ibid. 46：526.
Courregelongue, J. and Maffrand, J. P. 1989. Process for elimination cholesterol contained in a fatty substance of animal origin, and the fatty substance with reduced cholesterol obtained. US patent, 4, 880, 573.
Conrad, U. 1954. Newer concepts of lanolin composition. 日本化粧品技術者會誌5：11-22.
Crevreul, M. E.1856. Comptes Rendus 42: 130.
D’Abramo, L. R., Bordner, C. E., Conklin, D. E. and Baum, N. A. 1984. Sterol requirement of juvenile lobsters, Hormarus sp. Aquaculture 42: 13-25.
D’Abramo, L. R., Wright, J. S., Wright, K. H., Bordner, C. E. and Conklin, D. E. 1985. Sterol requirement of cultured juvenile crayfish, Pacifastacus leniusculus. Aquaculture 49：245-255.
Defouw, C. L., Zabik, M. E. and Gray, J. I. 1981. Fractionated edible beef tallow as deep frying medium for french fries. Journal of Food Science 46：452.
Downing, D. T., Kranz, Z. H. and Murray K.E. 1960. Australian Journal of Chemistry 13: 80.
Downing, D. T., Kranz, Z. H. and Murray K.E. 1963. Australian Journal of Chemistry 16: 679.
Downing, D. T. 1964. Branched-chain fatty acids in lipids of the newly born lamb. Journal of lipid research 41: 210-5.
Ei-Zanati, E. M. and Khedr, M. A. 1991. Separation of saturated and unsaturated acids from rice bran oil. Journal of the American Oil Chemists' Society 68: 436.
Fawaz, F., Chaigneau, M., Puisieux. F., Lucien, G. 1973. Analysis of ointments, oils, and waxes. XIII. Lanolin composition. 2. nonhydroxylated acids of total lanolin and its various fractions. Annales Pharmaceutiques Francaises 31（3）: 217-26.
Fawaz, F., Miet, C., Puisieux. F., 1974. Analysis of ointments, oils, and waxes. XIV. Composition of lanolin. 3. Hydroxylated acids of total lanolin and its various fractions. Annales Pharmaceutiques Francaises 32（1）: 59-68.
Feuge, R. O., Gajee, B. B. and Lovegren, N. V. 1973. Cocoa butter-like fats from fractionated cottonseed oil：I. preparation. Journal of the American Oil Chemists' Society. 50: 50.
Gabriel, B. 1986. MS：Lanolin and derivatives. Cosmetic ＆ Toiletries, 101: 91～97.
Hartmann, F. 1868. Thesis. Gottingen.
Hisakazu, S., Toshiaki Y. and Hiroshi, U. 1976. Separation of wool fatty acid. Patent US 3983147.
Iseo. 1988. “Food fats and oils”, 6th ed. Institute of shortening and edible oils, INC., Washington, D. C. Food technology 7: 67.
IUPAC Standard Methods for the Analysis of Oils. 1987. Fats and Derivatives, edited by C. Paquot and A. Hautfenne, Blackwell Scientific Publications, Oxford.
Jacobson, G. A. 1967. Quality control of commercial deep fat frying. Food technology 21: 147.
Kanazawa, A., Tanaka, N., Teshima, S. I. and Kashiwada, K. I. 1971. Nutritional requirements of prawn-II：Requirement for sterols. Bulletin of the Japan Society. Science Fish 37: 211-215.
Kean, J. C., Castell, J. D., Boghen, A. G., D' Abramo, L. R. and Conklin, D. E. 1985. A re-evaluation of the lecithin and cholesterol requirements of juvenile lobster (Homarus americanus) using crab protein-based diets. Aquaculture 47：143-149.
Keen, D. D. and Hobman, P. G. Improvements in or relating to methods of removing sterols and / or other steroidal compounds from edible fats and / or oils from which such sterols and / or other steroidal compounds have been removed. European Patent Application EP 0329347A2.
Kohj, I. and Katsunci, D. 1976. Wool alcohols and fatty acids. Patent JP 76139806.
Klaus Beneke and Gerhard Lagaly Institute of Inorganic Chemistry
Christiana Albertina University D-24098 Kiel. 2002. From Fuller´s Earth to Bleaching Earth: A Historical Note. European Clay Group Association Newsletter 5: 57-78.
Lanzani, A., Bondioli, P., Maiani, C., Folegatti, L., Venturini, S., Fedel, E. and Barretteau, P. 1994. A new short-path distillation system applied to the reduction of cholesterol in butter. Journal of the American Oil Chemists' Society 71: 609.
Liebrich, B. 1882. German patent 22: 516.
Lower, E. S. 1947. Wool wax alcohols in cosmetics. Amer. Perf. 49: 659.
Lower, E.S. 1956. Liquid lanolin. Perf Essent Oil Rec 47: 403-404.
Lower, E.S., Cressey S. 1957. Liquid lanolin. Drug Cosm Ind 81: 450.

Mancini-Filho, J., Smith, L. M., Creveling, R. K. and Al-Shaikh, H. F. 1986. Effects of selected chemical treatments on quality of fats used for deep frying. Journal of the American Oil Chemists' Society 63：1452.
Martha, W. 1976. The Merck Index. An Encyclopedia of Chemicals and
drugs. 9th ed., p. 996..
Murry, K. E. and Schoenfeld, R. 1955. Waxes. IX. The normal alchohol of wool wax. Australian Journal of chemistry 8: 424-31.
Miers, H. A. 1927. Growth of crystals in unsaturated liquids. Journal of the Institute of Metals 37: 331.
Pelick, N., Shigley, J. W. 1967. The fatty acid of degras. Journal of the American oil chemistry society 44（2）, 121-5.
Ponat, A. and Adelung, D. 1983. Studies to establish an optimal diet for carcinus maenas 3. vitamin and quantitative lipid requirements. Advances in Marine Biology 74：225-279.
Puri, S. P. 1980. Winterization of oils and fats. Journal of the American Oil Chemists' Society 848A-850A.
Russell, K. L., Hoch, S. 1962. Clear detergent solutions containing lanolin oil. Drug Cosm. Ind. 90: 294.
SAS. 1988. SAS User’s Guide：Basic Statistical Analysis. SAS Institute Inc., Cary, North Carolina.
Schulze, H. and Ztscher. 1970. Chemistry pp.453.
Siew, W. L. and Yassin, M. 1989. Effects of refining on chemical and physical properties of palm oil products. Journal of the American Oil Chemists' Society 66: 1116.
Siew, W. L., Tan, Y. A. and Tang, T. S. 1994. Silica refining of palm oil. Journal of the American Oil Chemists' Society 71: 1023.
Sliverman, M. 1962. Drug and Cosmet. Ind. 90: 292.
Sunde, C. J. 1956. Fractionation of lanolin oil. U.S. Patent 2,758,125
Sunde, C. J. and Richey, T. B. 1966. Purification of acylated lanoline products. U.S. Patent 3,272,851.
Sunde, C. J. 1970. Process for producing wool wax alcohols and fatty acids. U.S. Patent 3526647.
Teshima, S. and Kanazawa, A. 1971a. Biosynthesis of sterols in the lobster, Panulirus japonica, the prawn, Penaeus japonicus and the crab Portunus trituberculatus. Comparative Biochemistry and Physiology 38B: 597-602.
Teshima, S. and Kanazawa, A. 1971b. Utilization and biosynthesis of sterols in Artemia saline. Bulletin of the Japan Society of Science Fish 39: 1309-1314.
Teshima, S. and Kanazawa, A., 1973. Biosynthesis of sterols from demosterol in a mussel, Mytilus edulis. Bulletin of the Japan Society of Science Fish 39: 1309-1314.
Teshima, S. and Kanazawa, A. 1983. Digestibility of dietary lipids in the prawn. Bulletin of the Japan Society of Science. Fish 49：963-966.
Truter, E. V., 1951. The constitution of wool wax. Quarterly Review Chemistry Socience 5: 390-404.
Truter, E. V. 1955. The extraction of cholesterol from wool wax alcohols. Manufacturing Chemist and Aerosol News 26: 531-535.
Truter, E. V. 1956. Wool wax chemistry and technology. Willey-Interscience Publishers, New York.
Truter, E. V., 1962. The activities of some water-in-oil emulsifying agents. Journal of the society of cosmetic chemistry. 13, 173-87.
Traitler, H., Will, H. J. and Studer, A. 1988. Fractionation of black currant seed oil. Journal of the American Oil Chemists' Society 65：755-760.
Waltking, A. E. and Wessels, H. 1981. Chromatographic separation of polar and nonpolar components of frying fats. JAAC. 64: 1329.
Wang, F. S. and Lin, C. W. 1995. Turbidmetry for crystalline fractionation of lard. Journal of the American Oil Chemists' Society 72：585.
Weitkamp, A. W. 1945. Acidic constituents of degras, new method of structure elucidation. Journal of the American Chemical Society 67: 447.
Wheatley, V. R. 1963. Proceedings of the Leeds Philosophical and Literary Society. Scientific Section, T.G.A., (40), Dec.
Yang, M. H., Chang, S. C. and Chen, R. H. 1992. Effect of solvent polarity and fractionation temperature one the physicochemical properties of squid viscera strain. Journal of the American Chemical Society 69：1192.
Yates, R. A. and Caldwell, J. d. 1992. Adsorption capacity of active filter aids for cooking oil. Journal of the American Chemical Society 69: 804.
Yates, R. A. and Caldwell, J. d. 1993. Regeneration of oil used for deep frying：A comparison of active filter aids. Journal of the American Chemical Society 70：507
Yokochi. T., Usita, M.T., Kamisake, Y., Nakahare, T. and Suzuki, O. 1990. Increase in the γ-linolenic acid content by solvent winterization of fungal oil extracted from mortierella genus. Journal of the American Chemical Society 67：846.
Zurkowski, P. 1964. A rapid method for cholesterol determination with a single reagent. Clinical Chemistry 101: 451-453.