EPA和DHA的分离研究进展
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摘要
目前,EPA和DHA主要的生产来源是深海鱼油,但其含量较低不能直接满足食品和制药业的需求,富集提纯EPA和DHA尤为重要。简述了EPA和DHA的分离研究进展,主要从富集和高纯度单体的制备两个方面展开,系统介绍了低温结晶法、尿素包合法、分子蒸馏法、超临界流体萃取法、银离子络合法、脂肪酶法、高效液相色谱法、超临界流体色谱法、模拟移动床色谱法的分离原理以及近年的研究成果,并比较了各种方法的优缺点。最后对EPA和DHA提纯分离发展前景提出了展望,两种或多种分离方法组合是发展趋势,脂肪酶法和模拟移动床色谱法值得进一步深入研究。
The main sources of EPA and DHA production are marine fish oils. Low content of them in marine fish oils can't meet the needs of the food and pharmaceutical industries. Therefore,it is more and more important to enrich and purify EPA and DHA. The advance in purification and separation of EPA and DHA were reviewed from the aspects of enrichment and high purity monomer preparation. The separation principle and research results in recent years of the methods of low temperature crystallization,urea complexation,molecular distillation,supercritical fluid extraction,silver ion complexation,enzymatic purification,high performance liquid chromatography,supercritical fluid chromatography,simulated moving bed chromatography were systematically introduced. Besides,the advantages and disadvantages of these methods were described. The prospect of EPA and DHA separation was proposed. The combination of two kinds and multiple of separation methods was the development trend. The method of enzymatic purification and simulated moving bed chromatography deserved further study.
The main sources of EPA and DHA production are marine fish oils. Low content of them in marine fish oils can't meet the needs of the food and pharmaceutical industries. Therefore,it is more and more important to enrich and purify EPA and DHA. The advance in purification and separation of EPA and DHA were reviewed from the aspects of enrichment and high purity monomer preparation. The separation principle and research results in recent years of the methods of low temperature crystallization,urea complexation,molecular distillation,supercritical fluid extraction,silver ion complexation,enzymatic purification,high performance liquid chromatography,supercritical fluid chromatography,simulated moving bed chromatography were systematically introduced. Besides,the advantages and disadvantages of these methods were described. The prospect of EPA and DHA separation was proposed. The combination of two kinds and multiple of separation methods was the development trend. The method of enzymatic purification and simulated moving bed chromatography deserved further study.
引文
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[2]RUSSELL F D,BRGIN-MAUNDER C S.Distinguishing health benefits of eicosapentaenoic and docosahexaenoic acids[J].Mar Drugs,2012,10(11):2535-2559.
[3]罗庆华,宋英杰,王海磊,等.低温结晶法富集鳡鱼内脏油中多不饱和脂肪酸[J].中国油脂,2015,40(10):36-39.
[4]MORALES-MEDINA R,DE LEON G,MUNIO M,et al.Mass transfer modeling of sardine oil polyunsaturated fatty acid(PUFA)concentration by low temperature crystallization[J].J Food Eng,2016,183:16-23.
[5]李和,李佩文,杨亦平.低温结晶富集鱼油中EPA与DHA的方法[J].中国海洋药物,1997(4):50-52.
[6]LEI Q,BA S,ZHANG H,et al.Enrichment of omega-3fatty acids in cod liver oil via alternate solvent winterization and enzymatic interesterification[J].Food Chem,2016,199:364-371.
[7]ZHANG Y,WANG X S,XIE D,et al.One-step concentration of highly unsaturated fatty acids from tuna oil by low-temperature crystallization[J].J Am Oil Chem Soc,2017,94(3):475-483.
[8]LIU S C,ZHANG C H,HONG P Z,et al.Concentration of docosahexaenoic acid(DHA)and eicosapentaenoic acid(EPA)of tuna oil by urea complexation:optimization of process parameters[J].J Food Eng,2006,73(3):203-209.
[9]WANASUNDARA U N,SHAHIDI F.Concentration of omega 3-polyunsaturated fatty acids of seal blubber oil by urea complexation:optimization of reaction conditions[J].Food Chem,1999,65(1):41-49.
[10]吕微,蒋剑春,徐俊明.从脂肪酸的尿素包合法固相物中回收尿素的工艺[J].化工进展,2012,31(1):201-207.
[11]ROSSI P C,PRAMPARO M D C,GAICH M C,et al.Optimization of molecular distillation to concentrate ethyl esters of eicosapentaenoic(20∶5 omega-3)and docosahexaenoic acids(22∶6 omega-3)using simplified phenomenological modeling[J].J Sci Food Agric,2011,91(8):1452-1458.
[12]刘汝萃,王彩华,刘锡潜,等.一种高度不饱和脂肪酸鱼油的工业化生产方法:CN106753817A[P].2017-05-31.
[13]孙永利,卢伟,肖晓明,等.C16、C18混合脂肪酸分离技术研究进展[J].化工进展,2014,33(12):3139-3143.
[14]刘卓华,刘书成,田树良,等.硝酸银络合法浓缩金枪鱼鱼油多不饱和脂肪酸的研究[J].湛江海洋大学学报,2004,24(4):33-37.
[15]SHANMUGAM K,DONALDSON A A.Extraction of EPA/DHA from 18/12 EE fish oil using Ag NO3(aq):composition,yield,and effects of solvent addition on interfacial tension and flow pattern in mini-fluidic systems[J].Ind Eng Chem Res,2015,54(33):8295-8301.
[16]RIHA V,BRUNNER G.Phase equilibrium of fish oil ethyl esters with supercritical carbon dioxide[J].J Supercrit Fluids,1999,15(1):33-50.
[17]刘伟民,马海乐,李国文.超临界CO2连续浓缩鱼油EPA和DHA的研究[J].农业工程学报,2003,19(2):167-170.
[18]MASCHIETTI M,PEDACCHIA A.Supercritical carbon dioxide separation of fish oil ethyl esters by means of a continuous countercurrent process with an internal reflux[J].J Supercrit Fluids,2014,86(1):76-84.
[19]石红旗,缪锦来,李光友,等.脂肪酶催化水解法浓缩鱼油DHA甘油酯的研究.[J].中国海洋药物,2001,20(4):15-21.
[20]杨博,杨继国,吕扬效,等.脂肪酶催化鱼油醇解富集EPA和DHA的研究[J].中国油脂,2005,30(8):64-67.
[21]李金章,王玉明,薛长湖,等.脂肪酶催化乙酯甘油酯酯交换制备富含EPA和DHA的甘油三酯[J].中国油脂,2011,36(1):13-16.
[22]朱东奇,李道明,王卫飞,等.两步酶法合成富含EPA/DHA甘油酯的研究[J].中国油脂,2016,41(12):46-49.
[23]LIN W,WU F W,YUE L,et al.Combination of urea complexation and molecular distillation to purify DHA and EPA from sardine oil ethyl esters[J].J Am Oil Chem Soc,2014,91(4):687-695.
[24]PERRUT M.Purification of polyunsaturated fatty acid(EPA and DHA)ethyl esters by preparative high performance liquid chromatography[J].Lc Gc,1988,6(10):914-920.
[25]王学彤,张书圣,白吉洪,等.高效液相色谱法分离制备鱼油中的EPA和DHA[J].分析试验室,1999,18(1):44-47.
[26]HAO L P,CAO X J,HUR B K.Separation of single component of EPA and DHA from fish oil using silver ion modified molecular sieve 13X under supercritical condition[J].J Ind Eng Chem,2008,14(5):639-643.
[27]DILLON J T,APONTE J C,TAROZO R,et al.Purification of omega-3 polyunsaturated fatty acids from fish oil using silver-thiolate chromatographic material and high performance liquid chromatography[J].J Chromatogr A,2013,1312(17):18-25.
[28]邢飞,朱靖博,丁燕,等.载银氨基硅胶柱分离EPA和DHA的研究[J].中国油脂,2014,39(9):71-73.
[29]陈伟珠,洪专,赵敏,等.鱼油中二十碳五烯酸乙酯和二十二碳六烯酸乙酯的超临界流体色谱分离技术[J].食品科学,2012,33(24):82-85.
[30]MON~TANS F,CATCHPOLE O J,TALLON S,et al.Semipreparative supercritical chromatography scale plant for polyunsaturated fatty acids purification[J].J Supercrit Fluid,2013,79(1):46-54.
[31]任其龙,苏宝根,熊任天,等.EPA和DHA在超临界流体色谱柱中的传质动力学[J].化工学报,2001,52(9):788-792.
[32]杨亦文,吴彩娟,王宪达,等.超临界流体色谱法制备高纯度EPA-EE和DHA-EE[J].高校化学工程学报,2004,18(3):293-296.
[33]任其龙,鲍宗必,李敏,等.一种超临界色谱制备高纯度EPA酯和DHA酯单体的方法:CN104557542A[P].2015-04-29.
[34]FARIA R P,RODRIGUES A E.Instrumental aspects of simulated moving bed chromatography[J].J Chromatogr A,2015,1421:82-102.
[35]宋磊.模拟移动床色谱分离天然产物的研究[D].福建厦门:厦门大学,2013.
[36]LI M,BAO Z B,XING H B,et al.Simulated moving bed chromatography for the separation of ethyl esters of eicosapentaenoic acid and docosahexaenoic acid under nonlinear conditions[J].J Chromatogr A,2015,1425:189-197.
[37]任其龙,鲍宗必,李敏,等.一种模拟移动床色谱制备高纯度EPA酯和DHA酯单体的方法:CN104529772A[P].2015-04-22.
[2]RUSSELL F D,BRGIN-MAUNDER C S.Distinguishing health benefits of eicosapentaenoic and docosahexaenoic acids[J].Mar Drugs,2012,10(11):2535-2559.
[3]罗庆华,宋英杰,王海磊,等.低温结晶法富集鳡鱼内脏油中多不饱和脂肪酸[J].中国油脂,2015,40(10):36-39.
[4]MORALES-MEDINA R,DE LEON G,MUNIO M,et al.Mass transfer modeling of sardine oil polyunsaturated fatty acid(PUFA)concentration by low temperature crystallization[J].J Food Eng,2016,183:16-23.
[5]李和,李佩文,杨亦平.低温结晶富集鱼油中EPA与DHA的方法[J].中国海洋药物,1997(4):50-52.
[6]LEI Q,BA S,ZHANG H,et al.Enrichment of omega-3fatty acids in cod liver oil via alternate solvent winterization and enzymatic interesterification[J].Food Chem,2016,199:364-371.
[7]ZHANG Y,WANG X S,XIE D,et al.One-step concentration of highly unsaturated fatty acids from tuna oil by low-temperature crystallization[J].J Am Oil Chem Soc,2017,94(3):475-483.
[8]LIU S C,ZHANG C H,HONG P Z,et al.Concentration of docosahexaenoic acid(DHA)and eicosapentaenoic acid(EPA)of tuna oil by urea complexation:optimization of process parameters[J].J Food Eng,2006,73(3):203-209.
[9]WANASUNDARA U N,SHAHIDI F.Concentration of omega 3-polyunsaturated fatty acids of seal blubber oil by urea complexation:optimization of reaction conditions[J].Food Chem,1999,65(1):41-49.
[10]吕微,蒋剑春,徐俊明.从脂肪酸的尿素包合法固相物中回收尿素的工艺[J].化工进展,2012,31(1):201-207.
[11]ROSSI P C,PRAMPARO M D C,GAICH M C,et al.Optimization of molecular distillation to concentrate ethyl esters of eicosapentaenoic(20∶5 omega-3)and docosahexaenoic acids(22∶6 omega-3)using simplified phenomenological modeling[J].J Sci Food Agric,2011,91(8):1452-1458.
[12]刘汝萃,王彩华,刘锡潜,等.一种高度不饱和脂肪酸鱼油的工业化生产方法:CN106753817A[P].2017-05-31.
[13]孙永利,卢伟,肖晓明,等.C16、C18混合脂肪酸分离技术研究进展[J].化工进展,2014,33(12):3139-3143.
[14]刘卓华,刘书成,田树良,等.硝酸银络合法浓缩金枪鱼鱼油多不饱和脂肪酸的研究[J].湛江海洋大学学报,2004,24(4):33-37.
[15]SHANMUGAM K,DONALDSON A A.Extraction of EPA/DHA from 18/12 EE fish oil using Ag NO3(aq):composition,yield,and effects of solvent addition on interfacial tension and flow pattern in mini-fluidic systems[J].Ind Eng Chem Res,2015,54(33):8295-8301.
[16]RIHA V,BRUNNER G.Phase equilibrium of fish oil ethyl esters with supercritical carbon dioxide[J].J Supercrit Fluids,1999,15(1):33-50.
[17]刘伟民,马海乐,李国文.超临界CO2连续浓缩鱼油EPA和DHA的研究[J].农业工程学报,2003,19(2):167-170.
[18]MASCHIETTI M,PEDACCHIA A.Supercritical carbon dioxide separation of fish oil ethyl esters by means of a continuous countercurrent process with an internal reflux[J].J Supercrit Fluids,2014,86(1):76-84.
[19]石红旗,缪锦来,李光友,等.脂肪酶催化水解法浓缩鱼油DHA甘油酯的研究.[J].中国海洋药物,2001,20(4):15-21.
[20]杨博,杨继国,吕扬效,等.脂肪酶催化鱼油醇解富集EPA和DHA的研究[J].中国油脂,2005,30(8):64-67.
[21]李金章,王玉明,薛长湖,等.脂肪酶催化乙酯甘油酯酯交换制备富含EPA和DHA的甘油三酯[J].中国油脂,2011,36(1):13-16.
[22]朱东奇,李道明,王卫飞,等.两步酶法合成富含EPA/DHA甘油酯的研究[J].中国油脂,2016,41(12):46-49.
[23]LIN W,WU F W,YUE L,et al.Combination of urea complexation and molecular distillation to purify DHA and EPA from sardine oil ethyl esters[J].J Am Oil Chem Soc,2014,91(4):687-695.
[24]PERRUT M.Purification of polyunsaturated fatty acid(EPA and DHA)ethyl esters by preparative high performance liquid chromatography[J].Lc Gc,1988,6(10):914-920.
[25]王学彤,张书圣,白吉洪,等.高效液相色谱法分离制备鱼油中的EPA和DHA[J].分析试验室,1999,18(1):44-47.
[26]HAO L P,CAO X J,HUR B K.Separation of single component of EPA and DHA from fish oil using silver ion modified molecular sieve 13X under supercritical condition[J].J Ind Eng Chem,2008,14(5):639-643.
[27]DILLON J T,APONTE J C,TAROZO R,et al.Purification of omega-3 polyunsaturated fatty acids from fish oil using silver-thiolate chromatographic material and high performance liquid chromatography[J].J Chromatogr A,2013,1312(17):18-25.
[28]邢飞,朱靖博,丁燕,等.载银氨基硅胶柱分离EPA和DHA的研究[J].中国油脂,2014,39(9):71-73.
[29]陈伟珠,洪专,赵敏,等.鱼油中二十碳五烯酸乙酯和二十二碳六烯酸乙酯的超临界流体色谱分离技术[J].食品科学,2012,33(24):82-85.
[30]MON~TANS F,CATCHPOLE O J,TALLON S,et al.Semipreparative supercritical chromatography scale plant for polyunsaturated fatty acids purification[J].J Supercrit Fluid,2013,79(1):46-54.
[31]任其龙,苏宝根,熊任天,等.EPA和DHA在超临界流体色谱柱中的传质动力学[J].化工学报,2001,52(9):788-792.
[32]杨亦文,吴彩娟,王宪达,等.超临界流体色谱法制备高纯度EPA-EE和DHA-EE[J].高校化学工程学报,2004,18(3):293-296.
[33]任其龙,鲍宗必,李敏,等.一种超临界色谱制备高纯度EPA酯和DHA酯单体的方法:CN104557542A[P].2015-04-29.
[34]FARIA R P,RODRIGUES A E.Instrumental aspects of simulated moving bed chromatography[J].J Chromatogr A,2015,1421:82-102.
[35]宋磊.模拟移动床色谱分离天然产物的研究[D].福建厦门:厦门大学,2013.
[36]LI M,BAO Z B,XING H B,et al.Simulated moving bed chromatography for the separation of ethyl esters of eicosapentaenoic acid and docosahexaenoic acid under nonlinear conditions[J].J Chromatogr A,2015,1425:189-197.
[37]任其龙,鲍宗必,李敏,等.一种模拟移动床色谱制备高纯度EPA酯和DHA酯单体的方法:CN104529772A[P].2015-04-22.