CN102887848A - Method for preparing lutein crystals from marigold ointment by catalytic saponification - Google Patents
Method for preparing lutein crystals from marigold ointment by catalytic saponification Download PDFInfo
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- CN102887848A CN102887848A CN2012104246904A CN201210424690A CN102887848A CN 102887848 A CN102887848 A CN 102887848A CN 2012104246904 A CN2012104246904 A CN 2012104246904A CN 201210424690 A CN201210424690 A CN 201210424690A CN 102887848 A CN102887848 A CN 102887848A
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- saponification
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- aztec marigold
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Abstract
The invention provides a method for preparing lutein crystals from marigold ointment by catalytic saponification. A mixture of one or more of KOH, NaOH, sodium methoxide and sodium ethylate and alkaline ionic resin is preferably used as a saponification catalyst, and small amounts of deionized water and low-polarity solvent are utilized to clean the lutein crystal crude product, wherein the low-polarity solvent is preferably one or more of petroleum ether, n-hexane and ethyl acetate. Compared with the traditional method, the method provided by the invention greatly reduces the organic cleaning solvent, simplifies the after-treatment technique, and reduces the environmental pollution. The preparation method of the lutein crystals has the advantage of simple and stable technique, and is suitable for industrial large-scale production; and the purity and yield of the prepared lutein crystals are respectively up to 82% and 90% above.
Description
Technical field
The present invention relates to the preparation field of xenthophylls, be specifically related to the method that a kind of catalysis saponification Flower of Aztec Marigold ointment prepares lutein crystal.
Background technology
Xenthophylls is a Carotenoids, extensively is present in the natural phant, such as vegetables, fruit, cereal and some algae etc., is present in especially in a large number in the petal of Flower of Aztec Marigold.Xenthophylls has stronger oxidation-resistance, can remove or be suppressed at the free radical that causes tissue injury and cell aging in the human body, and therefore can be used as food, medicine or healthcare products prevents the diseases such as senile visual deterioration, cardiovascular disorder, tumour.In addition, because xenthophylls has bright and lustrous, strong coloring force, the advantage such as being rich in nutrition, it is widely used as food colorant and nutrition-fortifying agent.This shows that xenthophylls can play important role in human daily life, its application breadth and depth will constantly be deepened, and therefore, the production method of exploitation and optimization xenthophylls will have great economic and social benefit.
Preparation method about lutein crystal, existing partial monopoly is reported both at home and abroad, introduced a kind of preparation method of lutein crystal such as the patent US5648564 of U.S. KEMIN company, this method is take propylene glycol as solvent, and at high temperature alkaline saponification adds the water filtration crystallization, wash the dry lutein crystal that gets, the final purity of this method only has about 70%, and yield is relatively low about 60%.US Patent No. 6743953 also reported a kind of from marigold extractum the method for separation and purification xenthophylls, this method has been used the solvent more than 5 kinds, and solvent-oil ratio is large, yield is low, actual application value is little.Chinese patent CN200710185292.0 has reported that also a kind of working concentration is the novel method that the alkaline solution of 10-30% prepares lutein crystal, the method adopts the free lutein in weak polar solvent (tetrahydrofuran (THF)) the extraction solid soap compound after saponification fully, then crystallization, washing, vacuum-drying obtain high-purity lutein crystal, and yield is about 85%.Yet these methods all need the alkaline solution of working concentration large (being generally about 40% in actual industrial production) to carry out saponification, have perhaps used multiple and/or a large amount of organic cleaning solvents, cause subsequent disposal complicated, the problems such as contaminate environment.
Summary of the invention
The purpose of this invention is to provide the method that a kind of catalysis saponification Flower of Aztec Marigold ointment prepares lutein crystal, need not to adopt the saponifying agent of large concentration, and the method is by selecting suitable cleaning solvent kind and suitable mixing, washing solvent ratios, greatly reduced the usage quantity of organic solvent, simplified the operation of subsequent disposal, environmental contamination reduction.
The invention provides the method that a kind of catalysis saponification Flower of Aztec Marigold ointment prepares lutein crystal, may further comprise the steps: i) Flower of Aztec Marigold ointment, saponification catalyzer and alcoholic solution are added in the reactor, under 40-90 ℃, carry out saponification reaction, wherein based on 1g Flower of Aztec Marigold ointment meter, the consumption of saponification catalyzer is 0.1-0.2g, and the consumption of alcoholic solution is 2-10ml; Ii) add deionized water, through stirring, crystallization is filtered, and obtains the xenthophylls crude product; Iii) with weak polar solvent washing xenthophylls crude product; And the xenthophylls crude product that iv) iii) obtains with absolute ethanol washing, drying obtains described lutein crystal.The drying of step I in v) can adopt vacuum or lyophilize.
Step I) alcoholic solution in is preferably one or more in ethanol, methyl alcohol and the Virahol; The saponification catalyzer for example is one or more in KOH, NaOH, sodium methylate, sodium ethylate or the alkali ion resin, is preferably one or more and alkali ion resin blend thing in KOH, NaOH, sodium methylate, the sodium ethylate.In the described alkali ion resin, the strong basicity ion exchange resin is favourable.As the example of alkali ion resin, such as mentioning the alkali ion resins such as D201 type, 201 types or D204 type, can use wherein one or more.When employed saponification catalyzer comprised the alkali ion resin, the consumption of alkali ion resin was the 1-10 % by weight of Flower of Aztec Marigold ointment weight.
In one embodiment, in step I) in, at first the saponification catalyst dissolution is formed solution in alcoholic solution, and then mix with the Flower of Aztec Marigold ointment.Further preferably, at first other saponification catalyst components except the alkali ion resin are dissolved in the solution that is made into the 1-10 % by weight in the alcoholic solution, is preferably the 5-10 % by weight, and then mix with the Flower of Aztec Marigold ointment.
Preferably, step I i) under 30-50 ℃, carry out, and preferably under 40 ℃, carry out.Stir speed (S.S.) is controlled at 20-60 rev/min, in order to accelerate crystallization velocity and improve productive rate.
The volume of the deionized water that adds in a preferred embodiment, step I i) be described alcoholic solution volume 0.8-1.5 doubly, preferably equate with described alcoholic solution volume.
In the present invention, preferred steps iii) in the weight ratio of employed weak polar solvent and xenthophylls crude product be 0.5-2.0:1, be preferably 0.8-1.5:1, more preferably 1:1.
In the present invention, the weak polar solvent of step I in ii) is preferably one or more in sherwood oil, normal hexane and the ethyl acetate.Further preferably, the weak polar solvent of step I in ii) is that volume ratio is the mixing solutions of 1:1-5 and the sherwood oil that is preferably 1:1-3 and ethyl acetate or normal hexane and ethyl acetate.
In the method for the invention, select the cleaning solvent of suitable species and ratio, reduced purification step, improved purity and the yield of product; And compare with traditional method, employed cleaning solvent greatly reduces, and has simplified like this operation of aftertreatment, has reduced the pollution to environment, also helps to amplify to produce.Simultaneously, the method also preferably adds the alkali ion resin and coordinates the saponification process, thereby has avoided the excessive problem of saponifying agent concentration in the traditional method.In addition, need not in the method to add the additives such as oxygenant, simplified the step of purifying.
In a word, lutein crystal preparation method provided by the present invention, its technique is simple, stable, is fit to industrial scale production.The lutein crystal purity and the yield that prepare by the method reach respectively more than 82% and 90%, considerably beyond the standard of xenthophylls as food colorant and nutrition-fortifying agent.
Embodiment
The below will the invention will be further described by specific embodiment, but scope of the present invention is not limited to this.
Embodiment 1
Take by weighing 100g total carotinoid content and be 15.2% Flower of Aztec Marigold ointment, mix with the methanol solution of sodium methylate of 200ml 5%, be heated to 65 ℃, then adding based on Flower of Aztec Marigold ointment quality is 2% strongly basic anionic resin D201, continue insulated and stirred, catalysis saponification reaction 7h.Add the 200ml deionized water, 40 ℃ of insulations, stir, crystallization is filtered, and obtains the lutein crystal crude product.
Using 30ml sherwood oil and ethyl acetate volume ratio is that 1: 1 mixing solutions washs the lutein crystal crude product of gained, use again the 30ml absolute ethanol washing, vacuum-drying obtains 14.2g lutein crystal powder, detect through HPLC, total carotinoid content is 91.23%, xenthophylls purity is 82.17%, and product yield is 93.42%.
Embodiment 2
Take by weighing 100g total carotinoid content and be 15.2% Flower of Aztec Marigold ointment, mix with the methanol solution of sodium methylate of 200ml 5%, be heated to 65 ℃, then adding based on Flower of Aztec Marigold ointment quality is 2% strongly basic anionic resin D204, continue insulated and stirred, catalysis saponification reaction 7h.Add the 200ml deionized water, 40 ℃ of insulations, stir, crystallization is filtered, and obtains the lutein crystal crude product.
Using 30ml normal hexane and ethyl acetate volume ratio is that 1: 1 mixing solutions washs the lutein crystal crude product of gained, use again the 30ml absolute ethanol washing, vacuum-drying obtains 13.4g lutein crystal powder, detect through HPLC, total carotinoid content is 89.43%, xenthophylls purity is 80.37%, and product yield is 88.15%.
Embodiment 3
Take by weighing 100g total carotinoid content and be 15.2% Flower of Aztec Marigold ointment, mix with the methanol solution of sodium methylate of 200ml 5%, be heated to 65 ℃, then adding based on Flower of Aztec Marigold ointment quality is 2% strongly basic anionic resin D204, continue insulated and stirred, catalysis saponification reaction 7h.Add the 200ml deionized water, 40 ℃ of insulations, stir, crystallization is filtered, and obtains the lutein crystal crude product.
Use 30ml sherwood oil and ethyl acetate volume ratio to wash as the mixing solutions of the 1:2 lutein crystal crude product to gained, use again the 30ml absolute ethanol washing, vacuum-drying obtains 12.2g lutein crystal powder, detect through HPLC, total carotinoid content is 93.43%, xenthophylls purity is 82.37%, and product yield is 80.26%.
Embodiment 4
Take by weighing 10Kg total carotinoid content and be 15.2% Flower of Aztec Marigold ointment, mix with the methanol solution of sodium methylate of 20L 5%, be heated to 65 ℃, then adding based on Flower of Aztec Marigold ointment quality is 2% strongly basic anionic resin D201, continue insulated and stirred, catalysis saponification reaction 7h adds the 20L deionized water, 40 ℃ of insulations, stir, crystallization is filtered, and obtains the lutein crystal crude product.
Use 3L sherwood oil and ethyl acetate volume ratio to wash as the mixing solutions of the 1:1 lutein crystal crude product to gained, adopt again the 3L absolute ethanol washing, vacuum-drying, obtain 1.39Kg lutein crystal powder, detect through HPLC, total carotinoid content is 90.23%, and xenthophylls purity is 82.27%, and product yield is 91.44%.
Claims (10)
1. a catalysis saponification Flower of Aztec Marigold ointment prepares the method for lutein crystal, may further comprise the steps:
I) Flower of Aztec Marigold ointment, saponification catalyzer and alcoholic solution are added in the reactor, carry out saponification reaction under 40-90 ℃, wherein based on 1g Flower of Aztec Marigold ointment meter, the consumption of saponification catalyzer is 0.1-0.2g, and the consumption of alcoholic solution is 2-10ml;
Ii) add deionized water, through stirring, crystallization is filtered, and obtains the xenthophylls crude product;
Iii) with weak polar solvent washing xenthophylls crude product;
The xenthophylls crude product that iv) iii) obtains with absolute ethanol washing, drying obtains described lutein crystal.
2. method according to claim 1 is characterized in that, step I) in alcoholic solution be in ethanol, methyl alcohol and the Virahol one or more; The saponification catalyzer is one or more in KOH, NaOH, sodium methylate, sodium ethylate or the alkali ion resin, is preferably one or more and alkali ion resin blend thing in KOH, NaOH, sodium methylate, the sodium ethylate; Described alkali ion resin is preferably one or more in D201 type, 201 types and the D204 type alkali ion resin.
3. method according to claim 2 is characterized in that, the consumption of alkali ion resin is the 1-10 % by weight of Flower of Aztec Marigold ointment weight.
4. each described method is characterized in that, in step I according to claim 1-3) in, at first the saponification catalyst dissolution is formed solution in alcoholic solution, and then mix with the Flower of Aztec Marigold ointment.
5. according to claim 2 or the method described in 3, it is characterized in that, at first other saponification catalyst components except the alkali ion resin are dissolved in the solution that is made into the 1-10 % by weight in the alcoholic solution and is preferably the 5-10 % by weight, and then mix with the Flower of Aztec Marigold ointment.
6. method according to claim 1 is characterized in that, step I i) under 30-50 ℃, carry out, and preferably under 40 ℃, carry out.
7. method according to claim 1 is characterized in that, step I i) in the volume of the deionized water that adds be described alcoholic solution volume 0.8-1.5 doubly, preferably equate with described alcoholic solution volume.
8. method according to claim 1 is characterized in that, step I ii) in the weight ratio of employed weak polar solvent and xenthophylls crude product be 0.5-2.0:1, be preferably 1:1.
9. each described method is characterized in that according to claim 1-8, and the weak polar solvent of step I in ii) is selected from one or more in sherwood oil, normal hexane and the ethyl acetate.
10. method according to claim 9 is characterized in that, the weak polar solvent of step I in ii) is that volume ratio is the sherwood oil of 1:1-5 and the mixing solutions of ethyl acetate or normal hexane and ethyl acetate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104686795A (en) * | 2013-12-09 | 2015-06-10 | 彰武禾丰农业发展有限责任公司 | Light and oxidation resistant lutein feed additive producing process using marigold ointment |
| CN106674074A (en) * | 2016-12-30 | 2017-05-17 | 华宝香精股份有限公司 | Preparation method of water-soluble lutein |
| CN111548294A (en) * | 2020-04-10 | 2020-08-18 | 天津大学 | Lutein methanol solvate crystal and preparation method thereof |
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| US5648564A (en) * | 1995-12-21 | 1997-07-15 | Kemin Industries, Inc. | Process for the formation, isolation and purification of comestible xanthophyll crystals from plants |
| US6689400B2 (en) * | 2001-01-30 | 2004-02-10 | Sabinsa Corporation | Process of obtaining compositions of stable lutein and lutein derivatives |
| WO2004018417A1 (en) * | 2002-08-26 | 2004-03-04 | Kancor Flavours And Extracts Ltd | An improved process for the preparation of xanthophyll crystals |
| US7179930B2 (en) * | 2004-01-16 | 2007-02-20 | Indus Biotech Private Limited | Process for isolating, purifying and formulating a stable, commercial grade Lutein paste from oleoresin |
| CN101130512A (en) * | 2007-08-31 | 2008-02-27 | 陕西天润植物化工有限公司 | Method for producing xanthophyll |
| CN101168522A (en) * | 2007-11-21 | 2008-04-30 | 河北晨光天然色素有限公司 | Method for preparing high purity lutein crystal from marigold oil resin |
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| US5648564A (en) * | 1995-12-21 | 1997-07-15 | Kemin Industries, Inc. | Process for the formation, isolation and purification of comestible xanthophyll crystals from plants |
| US6689400B2 (en) * | 2001-01-30 | 2004-02-10 | Sabinsa Corporation | Process of obtaining compositions of stable lutein and lutein derivatives |
| WO2004018417A1 (en) * | 2002-08-26 | 2004-03-04 | Kancor Flavours And Extracts Ltd | An improved process for the preparation of xanthophyll crystals |
| US7179930B2 (en) * | 2004-01-16 | 2007-02-20 | Indus Biotech Private Limited | Process for isolating, purifying and formulating a stable, commercial grade Lutein paste from oleoresin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104686795A (en) * | 2013-12-09 | 2015-06-10 | 彰武禾丰农业发展有限责任公司 | Light and oxidation resistant lutein feed additive producing process using marigold ointment |
| CN106674074A (en) * | 2016-12-30 | 2017-05-17 | 华宝香精股份有限公司 | Preparation method of water-soluble lutein |
| CN111548294A (en) * | 2020-04-10 | 2020-08-18 | 天津大学 | Lutein methanol solvate crystal and preparation method thereof |
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