米糠混合油中谷维素的提取工艺研究
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摘要
谷维素(Oryzanol)具有抗氧化、降血脂、促进皮肤微血管循环等作用,可用于食品、医学、化妆品等领域,已引起国内外广泛重视。本文研究了从米糠混合油提取谷维素的工艺,并对其抗氧化性进行研究。
本研究从米糠混合油出发,经过两次碱炼后,谷维素富集到二道碱炼皂脚中;再将皂脚溶解到甲醇溶液中,过滤后,以柠檬酸析出,将析出液抽滤即得谷维素粗品;精制得谷维素成品。
通过单因素实验优化确定一道碱炼工艺为:NaOH溶液浓度5%(w/v),油与正已烷比例为1:2,反应温度55℃,反应时间60min,一道碱炼降低6个酸价,谷维素损失率仅为3.6%;二道碱炼工艺为:NaOH溶液浓度为11%(w/v),反应温度60℃,反应时间120min,二道碱炼谷维素捕集率达到84.9%,精炼率为90.8%。利用响应面法对影响二道碱炼工艺条件进行了优化,结果如下:NaOH溶液浓度10.64%,反应温度59.2℃,反应时间106.7min,谷维素捕集率为86.8%。
研究了二道碱炼条件对米糠油品质的影响,并对优化条件下二道碱炼后米糠油品质进行了评价,二道碱炼后米糠油谷维素残留率为8.1%,比市售米糠油谷维素含量高。酸价为0.36mg KOH/g油,色泽Y33R3.0,均符合三级米糠油标准。
将二次皂脚溶解在甲醇溶液中,然后用柠檬酸析出,通过单因素实验优化确定酸析条件为:pH 6,柠檬酸浓度20%,酸析温度60℃,酸析时间30min,养晶温度20℃。对主要因素进行正交实验,得优化条件为:柠檬酸浓度20%,酸析温度65℃,酸析时间30min,最终谷维素得率为64.6%,纯度为99.6%。
采取两种方法脱除皂脚中的残留溶剂,一种为真空加热法,另外一种为常压加热法。均可以取得很好效果,溶剂残留可降到安全水平。
Oryzanol in rice bran oil can be used in food, medicine, cosmetics and other fields. In this paper, a new enrichment process of oryzanol in rice bran miscella was systematically studied, and its anti-oxidation ability was tested.
Extraction method in this paper is as follows: rice bran oil blended with hexane refined twice, oryzanol trapped into the soapstock of the second alkali refining; the soapstock dissolved in methanol prior to filtration; then the solution precipitated by citric acid and vaccum filtrated to give crude oryzanol. Final products is obtained by further purification.
Through single factor experiment, the optimal refining process was established:1) the first alkali refining: acid value reduction 6, NaOH concentration 5%(w/v), oil to hexane ratio 1:2, reaction temperature 55℃, reaction time 60min, under this condition, the loss rate of oryzanol is only 3.6%; 2) the second alkali refining: NaOH concentration 11%(w/v), reaction temperature 55℃, reaction time 60min, after treating under the best condition, the trapping rate of oryzanol can reach 84.9% and oil refining yield is 90.8%. The optimum preparation conditions optimized by RSM were as follows: NaOH concentration 10.64%(w/v), reaction temperature 59.19℃, reaction time 106.7min. Under these conditions, the trapping rate of oryzanol was 86.60%.
After the second alkali, the quality of the rice bran oil was evaluated. The retention of oryzanol in the oil was 8.13%, acidity value 0.3(KOH)(mg/g) and colour Y33R3.0, which has reached Grade 3 requirement of rice bran oil.
The soapstock dissolved in methanol was subjected to filtration followed by precipitation using citric acid. Through single factor experiment, the optimal conditions were determined as follows: Acid precipitation pH 6, citric acid concentration 20%, acid precipitation temperature 60℃, acid precipitation time 30min and crystal growing temperature 20℃.Orthogonal experiments were performed to determine the optimal condition: citric acid concentration 20%, acid precipitation temperature 65℃, acid precipitation time 30 min. Under this condition, oryzanol yield was 64.6%, purity was 99.6%. Oryzanol obtained were characterized with HPLC and IR spectroscopy.
Two methods, i.e. heating in vaccum under stirring and heating in normal pressure under stirring,were adopted to remove solvent. The former gives samples no-detectable of solvent. While when heating temperature was 70℃, strring for 5 min in the other method, the solvent residual can be reduced to industrially acceptable level.
本研究从米糠混合油出发,经过两次碱炼后,谷维素富集到二道碱炼皂脚中;再将皂脚溶解到甲醇溶液中,过滤后,以柠檬酸析出,将析出液抽滤即得谷维素粗品;精制得谷维素成品。
通过单因素实验优化确定一道碱炼工艺为:NaOH溶液浓度5%(w/v),油与正已烷比例为1:2,反应温度55℃,反应时间60min,一道碱炼降低6个酸价,谷维素损失率仅为3.6%;二道碱炼工艺为:NaOH溶液浓度为11%(w/v),反应温度60℃,反应时间120min,二道碱炼谷维素捕集率达到84.9%,精炼率为90.8%。利用响应面法对影响二道碱炼工艺条件进行了优化,结果如下:NaOH溶液浓度10.64%,反应温度59.2℃,反应时间106.7min,谷维素捕集率为86.8%。
研究了二道碱炼条件对米糠油品质的影响,并对优化条件下二道碱炼后米糠油品质进行了评价,二道碱炼后米糠油谷维素残留率为8.1%,比市售米糠油谷维素含量高。酸价为0.36mg KOH/g油,色泽Y33R3.0,均符合三级米糠油标准。
将二次皂脚溶解在甲醇溶液中,然后用柠檬酸析出,通过单因素实验优化确定酸析条件为:pH 6,柠檬酸浓度20%,酸析温度60℃,酸析时间30min,养晶温度20℃。对主要因素进行正交实验,得优化条件为:柠檬酸浓度20%,酸析温度65℃,酸析时间30min,最终谷维素得率为64.6%,纯度为99.6%。
采取两种方法脱除皂脚中的残留溶剂,一种为真空加热法,另外一种为常压加热法。均可以取得很好效果,溶剂残留可降到安全水平。
Oryzanol in rice bran oil can be used in food, medicine, cosmetics and other fields. In this paper, a new enrichment process of oryzanol in rice bran miscella was systematically studied, and its anti-oxidation ability was tested.
Extraction method in this paper is as follows: rice bran oil blended with hexane refined twice, oryzanol trapped into the soapstock of the second alkali refining; the soapstock dissolved in methanol prior to filtration; then the solution precipitated by citric acid and vaccum filtrated to give crude oryzanol. Final products is obtained by further purification.
Through single factor experiment, the optimal refining process was established:1) the first alkali refining: acid value reduction 6, NaOH concentration 5%(w/v), oil to hexane ratio 1:2, reaction temperature 55℃, reaction time 60min, under this condition, the loss rate of oryzanol is only 3.6%; 2) the second alkali refining: NaOH concentration 11%(w/v), reaction temperature 55℃, reaction time 60min, after treating under the best condition, the trapping rate of oryzanol can reach 84.9% and oil refining yield is 90.8%. The optimum preparation conditions optimized by RSM were as follows: NaOH concentration 10.64%(w/v), reaction temperature 59.19℃, reaction time 106.7min. Under these conditions, the trapping rate of oryzanol was 86.60%.
After the second alkali, the quality of the rice bran oil was evaluated. The retention of oryzanol in the oil was 8.13%, acidity value 0.3(KOH)(mg/g) and colour Y33R3.0, which has reached Grade 3 requirement of rice bran oil.
The soapstock dissolved in methanol was subjected to filtration followed by precipitation using citric acid. Through single factor experiment, the optimal conditions were determined as follows: Acid precipitation pH 6, citric acid concentration 20%, acid precipitation temperature 60℃, acid precipitation time 30min and crystal growing temperature 20℃.Orthogonal experiments were performed to determine the optimal condition: citric acid concentration 20%, acid precipitation temperature 65℃, acid precipitation time 30 min. Under this condition, oryzanol yield was 64.6%, purity was 99.6%. Oryzanol obtained were characterized with HPLC and IR spectroscopy.
Two methods, i.e. heating in vaccum under stirring and heating in normal pressure under stirring,were adopted to remove solvent. The former gives samples no-detectable of solvent. While when heating temperature was 70℃, strring for 5 min in the other method, the solvent residual can be reduced to industrially acceptable level.
引文
1.Thomas A,Wilsona,Robert J Nicolosia,et al.Rice bran oil and oryzanol reduce plasma lipid and lipoprotein cholesterol concentrations and aortic cholesterol ester accumulation to a greater extent than ferulic acid in hypercholesterolemic hamsters[J].Journal of Nutritional Biochemistry,2007(18):105-112
2.Patel M,Naik S N.γ-Oryzanol from Rice Bran Oil-A review[J].Journal of Scientific and Industrial Research,2008(63):569-578
3.Z Xu,J Godber.Purification and identification of components of gamma-oryzanol in rice bran oil[J].J Agric Food Chem,1999,47(7):27-28
4.Yamaguchi K,Suzuki K,et al.A new 2,3-benzodiazepine inhibition of changes induced by stress loading and hypothalamic stimulation[J].Physiol Pharmacol,1983,61(6):619-625.
5.Ishihara M.Effect of γ-oryzanol on serum lipid peroxide level and clinical symptoms of patients with climacteric disturbances[J].AsiaOcenaniaJ.Obatet Gynaecol,1984,10:317-323.
6.Ichimaru Y,Motiyama M,Ichimaru M,Gomita Y.Effects of gamma-oryzanol on gastric lesions and small intestinal propulsive activity in mice[J].Nippon Yakurigaku Zasshi.1984,84(6):537-542.
7.张明发,谷维素的抗溃疡药理与临床[J].中国医院药学杂志,1989,9(5):207-209
8.李燕华,安英娣.谷维素调脂作用临床观察[J].临床荟萃,2003,18(5):274
9.Carlos Aguilar-Garcia,Grace Gavino,Mercedes Baragano-Mosqueda,et al.Correlation of tocopherol,tocotrienol,γ-oryzanol and total polyphenol content in rice bran with different antioxidant capacity assays[J].Food Chemistry,2007(102):1228-1232
10.Willcox,J K,et al.Antioxidants and prevention of chronic disease[J].Critical Reviews in Food Science and Nutrition,2004(44):275-295.
11.Ji-Soo Lee,Jong Soo Kim,Hyeon Gyu Lee.γ-oryzanol-loaded calcium pectinnate microparticles reinforced with chitosan:Optimization and release characteristics[J].Colloids and Surfaces B:Biointerfaces,2009(70):213-217
12.Kahlon T S,Saunders R M,Sayre R N.Cholesterol-Lowering Effects of Rice Bran oil Oil Fractions in hypercholsterolemic hamsters[J].Cereal Chemistry,1992,69(5):48 5-489.
13.程俊文,阚建全,王储炎.米糠中谷维素的研究进展及在食品中的应用[J].粮食与食品 工业,2005,12(4):17-22
14.Hiraga Y,Nakata N,Jin H,et al.Efect of the rice bran-derived phytosterol cycloartenol farulic acid ester on the central nervous system[J].Arzneimittelforschung.1993,43(7):715-721.
15.许大申.谷维素研究的现状与展望[J].中国油脂,1981(S1):501-516
16.许仁溥,许大申.谷维素在食品中应用开发[J].粮食与油脂,1997(3):23-26
17.许仁溥.谷维素研制三十余年历程[J].粮食与油脂,2003(3):10-13
18.张根旺,刘景顺.油脂工业副产品综合利用[M].北京:中国财政经济出版社,1988
19.刘军海.米糠谷维素提取纯化方法研究进展[J].粮食与油脂,2007(11):1-6
20.Narayan A V.Extraction and purification of oryzanol from rice bran oil and rice bran oil soapstock[J].J Amer Oil Chem Soc,2006,83:663-670
21.魏安池.萃取法提取谷维素的研究[J].中国油脂,2000,25(2):49-50
22.Mahua Ghosh.Review on recent trends in rice bran oil processing[J].J Am Oil Chem Soc,2007,84:315-324
23.杜长安,冯仁栋.溶剂法萃取谷维素生产新工艺的研究[J].中国油脂,2003(11):78-82
24.A G Gopala Krishna.Effect of refining of crude rice bran oil on the retention of oryzanol in the refined oil[J].J Am Oil Chem Soc,2001,78:127-131
25.Chen Chao Rui,Wang LingYa,Wang Chih Hung.Supercritical carbon dioxide extraction of rice bran oil and column partition fractionation of γ-oryzanols[J].Separation and Purification Technology,2008(61):358-365
26.Naryan,Barhate,Indira,et al.Process for crystallization of oryzanol from oryzanol enriched fraction derived from rice bran oil soap stock[P].Brazil Patent,WO 2004/055040 A1
27.杜长安.溶剂法萃取谷维素的生产方法[P]-中国专利,ZL 021356106
28.王庆智.提高谷维素得率的工艺探讨[J].中国油脂,1988(3):51-53
29.行业动态.用米糠资源弥补食用油脂的不足[J].食品与发酵工业,2008,34(8):117
30.韩秀丽,张如意,马晓健,等.米糠的综合利用及其前景[J].农产品加工学刊,2007,7(7):62-64
31.Jamel S Hamada.Ultrafiltration of partially hydrolyzedrice bran protein to recover value-added products[J].J Am Oil Chem Soc,2000,77(7):779-784
32.曹国锋,龚任,王舒平,等.米糠资源开发利用的研究[J].粮食与饲料工业,2000(7):42-44
33.李子.米糠油畅销西方国家[J].粮食与饲料工业,1994(1):50
34.孙德明.米糠综合利用的开发研究[J].农林科技,2008(12):200-201
35.Gopala Krishna,A G.Nutritional components of rice bran oil in relation to processing[J].Lipid Technol,2002(14):80-84.
36.刘军海,刘斌,刘敏,等.米糠浸出和米糠油精炼技术研究新进展[J].中国油脂,2001,26(3):17-20
37.Gopala Krishna,A G,S Khatoon,et al.Effect of refining of crude rice bran oil on the retention of oryzanol in the refined oil[J].J Am Oil Chem Soc,2001(78):127-131
38.郑建仙.功能性食品[M].北京:中国轻工业出版社,1995
40.徐瑞根.从米糠油中提取谷维素[J].江西师范大学学报.1989,13(1):88-90
41.龚院生,姚惠源.米糠中γ-谷维醇测定方法的研究[J].郑州工程学院学报.2001(1):28-31
42.Andreas Miller.Coupled liquid chromatography-gas chromatography for the rapid analysis of γ-oryzanol in rice lipids[J].Journal of Chromatography A,2003(985):403-410
43.盛益民,胡跃福.谷维素捕集过程分析及改进[J].中国油脂,1995,20(1):60-61
44.Kiritsakis A,Kanavouras A,Kiritsakis K.Chemical analysis,quality control and packaging issues of olive oil[J].European Journal of Lipid Science and Technology,2002(104):628-638
45.Montgomery D C.Design and analysis of experiments[EB/OL].John Wiley & Sons:New York,1999
46.Peng L,Xu X,Mu H,et al.Production of structured phospholipids by lipase-catalyzed acidolysis:Optimization using response surface methodology[J].Enzyme and Microbial Technology,2002(31):523-532
47.罗淑年,于殿宇,史佳宁.富含谷维素的米糠油精炼方法研究[J].食品工业科技,2007,28(12):153-155
48.刘名治,刘燕燕.从米糠油二次皂脚中制取谷维素的研究[J].天然产物研究与开发,1997,9(3):77-80
49.Rajam L Soban Kumar D R.A novel process for physically refining rice bran oil through simultaneous degumming and dewaxing[J].J Am Oil Chem Soc,2005,82(3):213-220
2.Patel M,Naik S N.γ-Oryzanol from Rice Bran Oil-A review[J].Journal of Scientific and Industrial Research,2008(63):569-578
3.Z Xu,J Godber.Purification and identification of components of gamma-oryzanol in rice bran oil[J].J Agric Food Chem,1999,47(7):27-28
4.Yamaguchi K,Suzuki K,et al.A new 2,3-benzodiazepine inhibition of changes induced by stress loading and hypothalamic stimulation[J].Physiol Pharmacol,1983,61(6):619-625.
5.Ishihara M.Effect of γ-oryzanol on serum lipid peroxide level and clinical symptoms of patients with climacteric disturbances[J].AsiaOcenaniaJ.Obatet Gynaecol,1984,10:317-323.
6.Ichimaru Y,Motiyama M,Ichimaru M,Gomita Y.Effects of gamma-oryzanol on gastric lesions and small intestinal propulsive activity in mice[J].Nippon Yakurigaku Zasshi.1984,84(6):537-542.
7.张明发,谷维素的抗溃疡药理与临床[J].中国医院药学杂志,1989,9(5):207-209
8.李燕华,安英娣.谷维素调脂作用临床观察[J].临床荟萃,2003,18(5):274
9.Carlos Aguilar-Garcia,Grace Gavino,Mercedes Baragano-Mosqueda,et al.Correlation of tocopherol,tocotrienol,γ-oryzanol and total polyphenol content in rice bran with different antioxidant capacity assays[J].Food Chemistry,2007(102):1228-1232
10.Willcox,J K,et al.Antioxidants and prevention of chronic disease[J].Critical Reviews in Food Science and Nutrition,2004(44):275-295.
11.Ji-Soo Lee,Jong Soo Kim,Hyeon Gyu Lee.γ-oryzanol-loaded calcium pectinnate microparticles reinforced with chitosan:Optimization and release characteristics[J].Colloids and Surfaces B:Biointerfaces,2009(70):213-217
12.Kahlon T S,Saunders R M,Sayre R N.Cholesterol-Lowering Effects of Rice Bran oil Oil Fractions in hypercholsterolemic hamsters[J].Cereal Chemistry,1992,69(5):48 5-489.
13.程俊文,阚建全,王储炎.米糠中谷维素的研究进展及在食品中的应用[J].粮食与食品 工业,2005,12(4):17-22
14.Hiraga Y,Nakata N,Jin H,et al.Efect of the rice bran-derived phytosterol cycloartenol farulic acid ester on the central nervous system[J].Arzneimittelforschung.1993,43(7):715-721.
15.许大申.谷维素研究的现状与展望[J].中国油脂,1981(S1):501-516
16.许仁溥,许大申.谷维素在食品中应用开发[J].粮食与油脂,1997(3):23-26
17.许仁溥.谷维素研制三十余年历程[J].粮食与油脂,2003(3):10-13
18.张根旺,刘景顺.油脂工业副产品综合利用[M].北京:中国财政经济出版社,1988
19.刘军海.米糠谷维素提取纯化方法研究进展[J].粮食与油脂,2007(11):1-6
20.Narayan A V.Extraction and purification of oryzanol from rice bran oil and rice bran oil soapstock[J].J Amer Oil Chem Soc,2006,83:663-670
21.魏安池.萃取法提取谷维素的研究[J].中国油脂,2000,25(2):49-50
22.Mahua Ghosh.Review on recent trends in rice bran oil processing[J].J Am Oil Chem Soc,2007,84:315-324
23.杜长安,冯仁栋.溶剂法萃取谷维素生产新工艺的研究[J].中国油脂,2003(11):78-82
24.A G Gopala Krishna.Effect of refining of crude rice bran oil on the retention of oryzanol in the refined oil[J].J Am Oil Chem Soc,2001,78:127-131
25.Chen Chao Rui,Wang LingYa,Wang Chih Hung.Supercritical carbon dioxide extraction of rice bran oil and column partition fractionation of γ-oryzanols[J].Separation and Purification Technology,2008(61):358-365
26.Naryan,Barhate,Indira,et al.Process for crystallization of oryzanol from oryzanol enriched fraction derived from rice bran oil soap stock[P].Brazil Patent,WO 2004/055040 A1
27.杜长安.溶剂法萃取谷维素的生产方法[P]-中国专利,ZL 021356106
28.王庆智.提高谷维素得率的工艺探讨[J].中国油脂,1988(3):51-53
29.行业动态.用米糠资源弥补食用油脂的不足[J].食品与发酵工业,2008,34(8):117
30.韩秀丽,张如意,马晓健,等.米糠的综合利用及其前景[J].农产品加工学刊,2007,7(7):62-64
31.Jamel S Hamada.Ultrafiltration of partially hydrolyzedrice bran protein to recover value-added products[J].J Am Oil Chem Soc,2000,77(7):779-784
32.曹国锋,龚任,王舒平,等.米糠资源开发利用的研究[J].粮食与饲料工业,2000(7):42-44
33.李子.米糠油畅销西方国家[J].粮食与饲料工业,1994(1):50
34.孙德明.米糠综合利用的开发研究[J].农林科技,2008(12):200-201
35.Gopala Krishna,A G.Nutritional components of rice bran oil in relation to processing[J].Lipid Technol,2002(14):80-84.
36.刘军海,刘斌,刘敏,等.米糠浸出和米糠油精炼技术研究新进展[J].中国油脂,2001,26(3):17-20
37.Gopala Krishna,A G,S Khatoon,et al.Effect of refining of crude rice bran oil on the retention of oryzanol in the refined oil[J].J Am Oil Chem Soc,2001(78):127-131
38.郑建仙.功能性食品[M].北京:中国轻工业出版社,1995
40.徐瑞根.从米糠油中提取谷维素[J].江西师范大学学报.1989,13(1):88-90
41.龚院生,姚惠源.米糠中γ-谷维醇测定方法的研究[J].郑州工程学院学报.2001(1):28-31
42.Andreas Miller.Coupled liquid chromatography-gas chromatography for the rapid analysis of γ-oryzanol in rice lipids[J].Journal of Chromatography A,2003(985):403-410
43.盛益民,胡跃福.谷维素捕集过程分析及改进[J].中国油脂,1995,20(1):60-61
44.Kiritsakis A,Kanavouras A,Kiritsakis K.Chemical analysis,quality control and packaging issues of olive oil[J].European Journal of Lipid Science and Technology,2002(104):628-638
45.Montgomery D C.Design and analysis of experiments[EB/OL].John Wiley & Sons:New York,1999
46.Peng L,Xu X,Mu H,et al.Production of structured phospholipids by lipase-catalyzed acidolysis:Optimization using response surface methodology[J].Enzyme and Microbial Technology,2002(31):523-532
47.罗淑年,于殿宇,史佳宁.富含谷维素的米糠油精炼方法研究[J].食品工业科技,2007,28(12):153-155
48.刘名治,刘燕燕.从米糠油二次皂脚中制取谷维素的研究[J].天然产物研究与开发,1997,9(3):77-80
49.Rajam L Soban Kumar D R.A novel process for physically refining rice bran oil through simultaneous degumming and dewaxing[J].J Am Oil Chem Soc,2005,82(3):213-220