CN1312126C - Prepn of lutein fally ester and lutein - Google Patents
Prepn of lutein fally ester and lutein Download PDFInfo
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- CN1312126C CN1312126C CNB2005101117672A CN200510111767A CN1312126C CN 1312126 C CN1312126 C CN 1312126C CN B2005101117672 A CNB2005101117672 A CN B2005101117672A CN 200510111767 A CN200510111767 A CN 200510111767A CN 1312126 C CN1312126 C CN 1312126C
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- lutein
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- acid ester
- xenthophylls
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Abstract
The present invention discloses a process for preparing lutein fatty acid ester from marigold extract and preparing a refined lutein product from lutein fatty acid ester. After being dissolved by an alkane solvent, crude marigold extract is adsorbed by macroporous adsorption resin, the macroporous adsorption resin is eluted with a mixed liquid of a low-toxicity alkane solvent and a low-carbon alcohol solvent, the eluate after elution is evaporated in a rotary mode to recover the solvent, and the eluate is dried under reduced pressure and in vacuum to obtain lutein fatty acid ester with the content of 80 to 95%. The lutein fatty acid ester with the content of 80 to 95% is saponified for 2 hours under the condition of alcohol alkali, the reaction liquid is filtered, and the filter cake is washed with a low-carbon alcohol solvent and water and is dried in a vacuum to obtain lutein with the purity of 80 to 95%. The process has the advantages of simple technology and can be used for industrially producing lutein fatty acid ester and lutein with the content higher than 80%. The present invention has the advantages of recoverable and reusable solvent eluant, low cost, no pollution in purification process, no waste water and environmental protection.
Description
Technical field
The present invention relates to a kind of biological chemistry isolation technique, be specifically related to the method that a kind of absorption one chromatography chromatography separation and purification prepares the high purity lutein fatty acid ester and prepares high purity lutein through saponification.
Background technology
According to foreign study, xenthophylls content in deep green leaf vegetables such as wild cabbage, kale, spinach and flowers such as Potmarigold Calendula and Flower of Aztec Marigold is the highest.Secondly, then contain abundant fatty acid ester of lutein in pumpkin, peach, capsicum, mango, the oranges and tangerines, it is the same palmitinic acid of xenthophylls, the general name of the fatty acid ester of lutein that lipid acid such as tetradecanoic acid and lauric acid exist with esterified form.It is a kind of natural pigment that extensively is present in vegetables, flowers, fruit and some algae bio.
As far back as the mid-80 in last century, western medicine the researchist promptly find: the contained natural carotenol of plant is a kind of antioxidant of excellent performance.A certain amount of xenthophylls is joined in the food, can prevent a series of diseases that human body causes because of organ senescence, because xenthophylls is the same with the carotenoid that is named as " zeaxanthin ", have the radical of resisting and in human body, cause cell and organ damage, thereby can prevent cardiovascula arteriosclerosis, coronary heart disease and the tumor disease that body aging causes.Research is proof also: the visual deterioration that xenthophylls can prevent senile eyeball macula retinae to degenerate to cause is with blind.The annual whole world all has the old man of millions of over-65s to cause blurred vision and blind because of macular degeneration disease, if can in time in its food, replenish xenthophylls, can delay the vision degeneration and blind disease (the Seddon et al.J.Am.Med.Assoc.272 that cause because of macular degeneration, 1413-1420,1994).
To studies show that of xenthophylls chemical structure: it has 3 chiral centres, so 8 kinds of steric isomers (in fact only there is a kind of isomer in nature) are arranged.Because complete synthesis technology is too complicated, the xenthophylls of industrialization synthetic individual isomer is not success as yet so far.So have only the xenthophylls that from natural phant such as kale or Potmarigold Calendula, Flower of Aztec Marigold, extracts just to contain the active substance that really has antioxygenation at present.
U.S. Kai Ming food company (Kemin Food Co.) has taken the lead in inventing the novel process of producing xenthophylls, and (U.S.Patent 5,648,564), dissolve the marigold extractum of from marigold petal, extracting with propylene glycol, directly added 70 ℃ of saponification reactions of 45% potassium hydroxide aqueous solution 10 hours, washing the after-filtration lyophilize then, to obtain purity be about 70% xenthophylls highly finished product, and the total recovery of xenthophylls product is about 60%.Make xenthophylls become a kind of commercialization novel healthy food additive.
People such as Khachik in document (WO 99/20587) with directly lixiviate, saponification marigold petal under tetrahydrofuran (THF) and the ethanol/potassium hydroxide room temperature, vat liquor filters back underpressure distillation solvent evaporated, washing can obtain the xenthophylls highly finished product about 70% behind the washing with alcohol product.
(U.S.Patent 6 for people such as the Sunil Kumar T.K. of India, 743,953) adopted Virahol and 70 ℃ of saponification marigold extractum of potassium hydroxide 3 hours, solvent evaporated after washing filter cake, ethyl acetate extraction, the water back extraction is washed with n-hexane/acetone after the solvent evaporated, can obtain content after the methanol wash at 85% xenthophylls highly finished product, the total recovery of xenthophylls product is about 35%.
The medical expert confirms: (Khachik et al.Pure﹠amp is absorbed by the body fatty acid ester of lutein is become xenthophylls by the enzyme decomposition and inversion in people's small intestine after; Appl.Chem., 63 (1): 71-80,1991).So the same equal can use of fatty acid ester of lutein as new food additive with xenthophylls.The source of xenthophylls has been expanded in the extraction success of fatty acid ester of lutein greatly.
Extract fatty acid ester of lutein (commodity are called Xangold) from resourceful pumpkin with the tangerine slag after squeezing the juice as South America Henkle company.In addition, among the patent WO 03/037833 with supercritical CO
2Dried marigold flower lobe after extraction is pulverized can obtain the fatty acid ester of lutein about content 20-25%, and its extract yield can reach about 85%.
People such as Luis W.Levy are at U.S.Patent 6, adopt the marigold extractum stirring at room of extracting in the Virahol mixing marigold petal in 191,293, filter, the content of fatty acid ester of lutein in the marigold extractum can be brought up to 69% from 27.9% after the vacuum-drying, total recovery is about 50%.
The people (WO 02/094772) such as Quesnel Yannick of France adopt the marigold extractum of extracting in the acetone solution marigold petal, the propyl carbinol freezing and crystallizing, the method of washing with alcohol can obtain the fatty acid ester of lutein highly finished product about 80%, and total recovery is about 30%.
The present preparation method who can be used for suitability for industrialized production fatty acid ester of lutein and xenthophylls is solvent treatment method, owing to need a series of dissolving, precipitation, the crystalline operation, the yield of its technology is generally lower, and the solvent demand is big, kind is many, recycles difficulty.
Summary of the invention
It is simple to the objective of the invention is to set up a kind of technological operation, and solvent and leacheate are capable of circulation to be applied mechanically, and environmental friendliness is convenient to fairly large suitability for industrialized production and is extracted the method for preparing fatty acid ester of lutein and xenthophylls highly finished product.
For achieving the above object, the technical scheme that the present invention takes is to extract preparation fatty acid ester of lutein and xenthophylls highly finished product from marigold extractum, the steps include:
1) Flower of Aztec Marigold crude extract medicinal extract is dissolved after absorption with macroporous adsorbent resin is the eluent wash-out with the mixed solution of a kind of low-carbon alcohol kind solvent, a kind of low-carbon alcohol kind solvent and a kind of alkane solvents, a kind of alkane solvents successively by alkane solvents;
2) leacheate reclaims solvent through rotary evaporation, and can obtain content again after the reduced vacuum drying is 80-95% fatty acid ester of lutein highly finished product.
3) with above-mentioned content 80-95% fatty acid ester of lutein highly finished product saponification reaction 1～3 hour under pure alkali condition, filtering reacting liquid;
4) filter cake is through low-carbon (LC) alcohols and water washing vacuum-drying, and obtaining purity is the xenthophylls highly finished product of 80-95%.
The macroporous adsorbent resin skeleton structure that adopts in the aforesaid method is vinylbenzene-divinylbenzene or acrylate-divinylbenzene copolymer, specifically macroporous adsorbent resin is a kind of among the HZ-841 of HZ802, HZ-803, HZ-816, HZ-818 or acrylate-divinylbenzene skeleton structure of vinylbenzene-divinylbenzene skeleton structure, and specification is 50～100 orders.
Described low-carbon alcohol kind solvent can be methyl alcohol, ethanol or propyl alcohol etc.; Alkane solvents can be normal hexane, normal heptane or sherwood oil etc.
The pure alkali of described saponification process is the combined hybrid liquid of methyl alcohol or ethanol and sodium hydroxide or potassium hydroxide, and temperature is between 20 ℃～60 ℃.
Positively effect of the present invention is: the inventive method technology is simple, the total recovery height, and the eluent solvent agent is recyclable applies mechanically, and cost is low, and purge process is pollution-free, compliance with environmental protection requirements.Because xenthophylls itself is being rich in nutrition, the prevention human senility is had good effect, so xenthophylls and fatty acid ester of lutein are in very great demand in the international market, the vast market prospect that implements of the present invention.
Embodiment
Flower of Aztec Marigold crude extract medicinal extract among the present invention can use the commercially available product that contains fatty acid ester of lutein 20%-30%, and used solvent is analytical pure, and water is deionized water.The efficient liquid phase chromatographic analysis acetonitrile, methyl alcohol, ethyl acetate, water is chromatographically pure.Raw material and product analysis high pressure liquid chromatograph are the HP/Agilent1100 type, and chromatographic column is HP/Agilent4.6 * 100mmC
18Post, 3.5 μ m.Macroporous adsorbent resin is the commercially available prod of Shanghai Huazhen Science and Technology Co., Ltd., is the HZ802 of vinylbenzene-divinylbenzene as skeleton structure, HZ803, and HZ816, HZ818, also can adopt skeleton structure is product HZ841 of acrylate-divinylbenzene etc.Rotary Evaporators BC-R2001 is the triumphant Science and Technology Ltd. of a last sea cowry product, and it is Shanghai the 3rd analytical instrument factory product that spectrophotometric is counted 722 type grating beam splitting photometers.
The content assaying method of fatty acid ester of lutein can be referring to Chinese patent CN 1432567A
The content assaying method of xenthophylls is analyzed the AOAC of association method 970.64 referring to the U.S.
By can helping the understanding of the present invention, and do not limit content of the present invention to following embodiment.
Embodiment 1
Stir following fatty acid ester of lutein 21.2% Flower of Aztec Marigold crude extract medicinal extract 50 grams that will contain and be dissolved in the normal hexane of 50ml, wait to dissolve complete back standby.
With about 300 grams of macroporous adsorbent resin HZ-802 (conventional treatment method according to ion exchange resin and the polymeric adsorbent is handled) diameter of handling well of packing into is 5cm, and length is in the glass column of 100cm, and the lower end is a teflon piston.The husky core of piston upper end is No. 2 husky cores.With feeding in the glass column under the complete mixture room temperature of above-mentioned dissolving, led in about 10 minutes, use a) ethanol of 1000ml successively; B) normal hexane of 2500ml: the mixed solution of ethanol=2: 1; C) the normal hexane drip washing of 1000ml gets a, b, three kinds of component leacheates of c, respectively by Rotary Evaporators evaporated under reduced pressure solvent, wherein the b part can get about 9 grams of orange red oily matter, can separate out orange red solid after freezing, vacuum-drying gets 8.2 grams under the room temperature after 24 hours, and detection level is 91.5%.A, the c component does not all contain fatty acid ester of lutein, available Rotary Evaporators decompression and solvent recovery.
Embodiment 2
Stir following fatty acid ester of lutein 21.2% Flower of Aztec Marigold crude extract medicinal extract 50 grams that will contain and be dissolved in the sherwood oil (60-90 ℃) of 50ml, wait to dissolve complete back standby.
With about 300 grams of macroporous adsorbent resin HZ-816 (conventional treatment method according to ion exchange resin and the polymeric adsorbent is handled) diameter of handling well of packing into is 5cm, and length is in the glass column of 100cm, and the lower end is a teflon piston.The husky core of piston upper end is No. 2 husky cores.With feeding in the glass column under the complete mixture room temperature of above-mentioned dissolving, led in about 10 minutes, use a) methyl alcohol of 1000ml successively; B) sherwood oil of 2500ml (60-90 ℃): the mixed solution of methyl alcohol=2: 1; C) sherwood oil of 1000ml (60-90 ℃) drip washing, get a, b, three kinds of component leacheates of c, by Rotary Evaporators evaporated under reduced pressure solvent, wherein the b part can get about 10 grams of orange red oily matter respectively, can separate out orange red solid after freezing, vacuum-drying gets 9.1 grams under the room temperature after 24 hours, and detection level is 85.7%.A, the c component does not all contain fatty acid ester of lutein, available Rotary Evaporators decompression and solvent recovery.
Embodiment 3
Make fatty acid ester of lutein 21.2% Flower of Aztec Marigold crude extract dissolving mixed solution by the method identical with embodiment 1, the employing macroporous adsorbent resin is HZ-841, and the leacheate proportioning changes into: a) methyl alcohol of 1000ml; B) normal hexane of 2500ml: methyl alcohol is 2: 1 mixed solution; C) 1000ml normal hexane.Other are by equipment identical with embodiment 1 and processing step operation, and b) the part leacheate can get orange red solid 8.5 grams, and detection level is 92%.A, the c component does not all contain fatty acid ester of lutein, available Rotary Evaporators decompression and solvent recovery.
Embodiment 4
Make fatty acid ester of lutein 21.2% Flower of Aztec Marigold crude extract mixed solution by the method identical with embodiment 1, the employing macroporous adsorbent resin is HZ-818.Other are by equipment identical with embodiment 1 and processing step operation, and b), the vacuum-drying freezing through underpressure distillation of part leacheate can get orange red solid 9.1 grams, and content is 93%.
Embodiment 5
The fatty acid ester of lutein highly finished product of getting the above-mentioned content 91.5% of 5 grams mix with 50ml ethanol and 6 gram sodium hydroxide, saponification reaction 2 hours under 60 ℃ of stirrings of temperature in being heated to, filtering reacting liquid, use the ethanol of 50ml and the water washing filter cake of 100ml respectively, vacuum-drying gets orange red crystal 2 .1 gram under the room temperature after 24 hours, and detection level is 94% xenthophylls highly finished product.
Embodiment 6
The fatty acid ester of lutein highly finished product of getting the above-mentioned content 92% of 5 grams mix with 50ml methyl alcohol and 8.4 gram sodium hydroxide, saponification reaction is 2 hours under 20 ℃ of following stirrings of room temperature, filtering reacting liquid, use the methyl alcohol of 50ml and the water washing filter cake of 100ml respectively, vacuum-drying gets orange red crystal 2 .2 gram under the room temperature after 24 hours, and detection level is 93% xenthophylls highly finished product.
Being rich in nutrition in view of xenthophylls itself, be a kind of superior antioxidant, can be anti-ageing; Fatty acid ester of lutein is absorbed by the body can be become xenthophylls by the enzyme decomposition and inversion in people's small intestine after, so xenthophylls and fatty acid ester of lutein all are commercially available prod salable.In the technical solution of the present invention, earlier through step 1), 2) prepare fatty acid ester of lutein from marigold extractum, again through step 3) 4) prepare the xenthophylls highly finished product from fatty acid ester of lutein.Be to be understood that; from marigold extractum through step 1), 2) preparation fatty acid ester of lutein; or from fatty acid ester of lutein through step 3) 4) preparation xenthophylls highly finished product, or from marigold extractum through step 1) 2) 3) 4) preparation xenthophylls highly finished product are all within protection domain of the present invention.
Claims (7)
1. the preparation method of fatty acid ester of lutein and xenthophylls is characterized in that:
1) Flower of Aztec Marigold crude extract medicinal extract is dissolved after absorption with macroporous adsorbent resin is the eluent wash-out with the mixed solution of a kind of low-carbon alcohol kind solvent, a kind of low-carbon alcohol kind solvent and a kind of alkane solvents, a kind of alkane solvents successively by alkane solvents;
2) leacheate reclaims solvent through rotary evaporation, and can obtain content again after the reduced vacuum drying is 80-95% fatty acid ester of lutein highly finished product;
3) with above-mentioned content 80-95% fatty acid ester of lutein highly finished product saponification reaction 1～3 hour under pure alkali condition, filtering reacting liquid;
4) filter cake is through low-carbon (LC) alcohols and water washing, vacuum-drying, and obtaining purity is the xenthophylls highly finished product of 80-95%.
2. the preparation method of fatty acid ester of lutein according to claim 1 and xenthophylls is characterized in that: described macroporous adsorbent resin skeleton structure is vinylbenzene-divinylbenzene or acrylate-divinylbenzene copolymer.
3. the preparation method of fatty acid ester of lutein according to claim 1 and 2 and xenthophylls is characterized in that: described macroporous adsorbent resin is a kind of among the HZ-841 of HZ802, HZ-803, HZ-816, HZ-818 or acrylate-divinylbenzene skeleton structure of vinylbenzene-divinylbenzene skeleton structure.
4. the preparation method of fatty acid ester of lutein according to claim 1 and xenthophylls is characterized in that: described macroporous adsorbent resin, its specification are 50～100 orders.
5. the preparation method of fatty acid ester of lutein according to claim 1 and xenthophylls is characterized in that being: described low-carbon alcohol kind solvent is methyl alcohol, ethanol or propyl alcohol; Alkane solvents is normal hexane, normal heptane or sherwood oil.
6. the preparation method of fatty acid ester of lutein according to claim 1 and xenthophylls is characterized in that: the pure alkali of described saponification process is the combined hybrid liquid of methyl alcohol or ethanol and sodium hydroxide or potassium hydroxide.
7. the preparation method of fatty acid ester of lutein according to claim 1 and xenthophylls is characterized in that: the temperature of described saponification reaction process is between 20 ℃～60 ℃.
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| CNB2005101117672A CN1312126C (en) | 2005-12-21 | 2005-12-21 | Prepn of lutein fally ester and lutein |
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| CNB2005101117672A CN1312126C (en) | 2005-12-21 | 2005-12-21 | Prepn of lutein fally ester and lutein |
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| CN1810785A CN1810785A (en) | 2006-08-02 |
| CN1312126C true CN1312126C (en) | 2007-04-25 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4067342A1 (en) | 2021-04-02 | 2022-10-05 | Kemijski Institut | Sustainable preparation of xanthophyll esters |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103091446B (en) * | 2013-01-31 | 2015-12-23 | 甘肃省农垦农业研究院 | Lutein ester saponification degree rapid assay methods |
| CN107082756B (en) * | 2017-03-17 | 2018-11-23 | 晨光生物科技集团股份有限公司 | A kind of industrial production process of lutein crystal |
| CN107338279A (en) * | 2017-09-01 | 2017-11-10 | 广州立达尔生物科技股份有限公司 | Lipase-catalyzed esterification produces lutein carboxylate |
| CN110563625B (en) * | 2019-09-29 | 2020-07-31 | 山东天音生物科技有限公司 | Method for separating and purifying zeaxanthin from marigold oleoresin |
| WO2022155338A1 (en) | 2021-01-14 | 2022-07-21 | Kemin Industries, Inc. | Process for crystallization of high purity lutein esters from marigold extracts |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1362894A (en) * | 2000-02-13 | 2002-08-07 | 巴布考克及威尔考克斯公司 | Circulating fluidized bed reactor with selective catalytic reduction |
| US6689460B2 (en) * | 2001-06-14 | 2004-02-10 | W. R. Grace & Co.-Conn. | Primer/membrane barrier system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1362894A (en) * | 2000-02-13 | 2002-08-07 | 巴布考克及威尔考克斯公司 | Circulating fluidized bed reactor with selective catalytic reduction |
| US6689460B2 (en) * | 2001-06-14 | 2004-02-10 | W. R. Grace & Co.-Conn. | Primer/membrane barrier system |
Non-Patent Citations (1)
| Title |
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| 叶黄素研究进展 许秀兰等，粮食与油脂，第10期 2004 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4067342A1 (en) | 2021-04-02 | 2022-10-05 | Kemijski Institut | Sustainable preparation of xanthophyll esters |
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