CN102349647B - Combination containing lutein ester and preparation method thereof - Google Patents

Combination containing lutein ester and preparation method thereof Download PDF

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CN102349647B
CN102349647B CN2011103052752A CN201110305275A CN102349647B CN 102349647 B CN102349647 B CN 102349647B CN 2011103052752 A CN2011103052752 A CN 2011103052752A CN 201110305275 A CN201110305275 A CN 201110305275A CN 102349647 B CN102349647 B CN 102349647B
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filter cake
adds
mixed solvent
alcohol
filter
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CN102349647A (en
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吴文忠
黄媛
徐维锋
范志强
吕忠武
刘强
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Dalian promise biological Limited by Share Ltd
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DALIAN INNOBIOACTIVES Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/24—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by six-membered non-aromatic rings, e.g. beta-carotene
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
    • A23L33/105—Plant extracts, their artificial duplicates or their derivatives

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Abstract

The invention relates to a combination containing lutein ester and a preparation method thereof. The preparation method comprises the steps of: decreasing the temperature of solution of a marigold extract solvent A to 20-28 DEG C, maintaining the temperature for 0.5-4 hours, decreasing the temperature to 5-18 DEG C, maintaining the temperature for 0.5-4 hours and filtering to obtain a filter cake I; and under the condition of 30-70 DEG C, dissolving the filter cake I in a mixed solvent A, agitating for 0.5-5 hours, decreasing the temperature to 10-28 DEG C, keeping the temperature for 0.5-5 hours, filtering to obtain a filter cake II and conducting subsequent steps, wherein the mixed solvent A is the mixed solvent of methyl acetate, acetic ether, n-propyl acetate or butyl acetate and C1-3 alcohol. By adopting the method provided by the invention, the process is simple and feasible, the industrialization is easy to realize, all operations are conducted at low temperature and the stability of the product is guaranteed. The yield of the obtained product highly reaches more than 25 percent, the content of total esters in the product is more than 70 percent, the content of trans-lutein highly reaches 90-93 percent and the bioactivity of the product during use is greatly improved.

Description

The composition and method of making the same that contains lutein ester
Technical field
The present invention relates to separate high-content lutein ester product from marigold extractum, especially have the method for the composition of high trans lutein ester content.Relate in particular to the method for utilizing the direct crystallization method to obtain the said products
Background technology
Lutein ester is a kind of carotenoid fatty acid ester that exists with lipid acid and xenthophylls combining form.It extensively is present in the plant materialss such as pumpkin, spinach, wild cabbage, marigold flower.Studies show that, the absorption lutein ester can improve the lutein levels in blood and macula retinae, thereby the prevention age related is looked yellow class degeneration and cataract, and can effectively suppress the generation of tumor growth and atherosclerosis.Xenthophylls and zeaxanthin are unique carotenoid that is present in the human retina macular area, and human body self can not synthesize xenthophylls and must replenish it by daily meals.The lutein ester of occurring in nature has two kinds of configurations, is respectively trans and cis, wherein take the alltrans molecular configuration as main.The alltrans lutein ester can be divided into again: xenthophylls monoesters and xenthophylls diester.
In the plant materialss such as Flower of Aztec Marigold, free lutein content is less, and by modifications such as lauric acid, myristic acid, palmitinic acids, the ester that wherein content is the highest is xenthophylls palmitinic acid diester (A Subagio NMorita.Food Reasearch internation mostly, 2001,34:315-320)
Figure BDA0000097512190000011
The applicant provides a kind of preparation, stable state and method for removing pollutant thereof of high purity lutein ester at CN101486671A: first the acetone insoluble matter in marigold extractum is removed, enriched material with imurity-removal carries out Virahol or butanol crystallizing again, uses at last the lower alcohol washing crystal again.Wherein the two-step crystallization solvent for use is different, exists certain solvent to intersect, and Virahol or butanol crystallizing used time are longer, are unfavorable for the lifting of production efficiency.The washing of final step lower alcohol exists a large amount of solvents to intersect with Virahol or butanols, and the product yield of the method is very low, only has 11～15%.The present invention has used for reference the method that wherein pollutant removing and antioxidant add, but the crystallization processes of core in this technical scheme carried out substantial improvement.
CN101891664A discloses a kind of method of purifying lutein esters, to use ethyl acetate that the Flower of Aztec Marigold ointment is fully dissolved rear heat filtering, add the dehydrated alcohol crystallization after removing insolubles, the filter cake that obtains with the oven dry of lower alcohol washing final vacuum, finally obtains the lutein ester product again.This method adds the dehydrated alcohol crystallization time up to the raising that was unfavorable for production efficiency in 16 hours.Selected propyl carbinol when the lower alcohol washing leaching cake, higher being difficult to of propyl carbinol boiling point is completely removed in the product vacuum drying, has hidden danger on safety when making product use in food ingredients.And not adding sorbent material to remove heavy metal and pesticide remnant when acetic acid ethyl dissolution filters, the finished product do not add the safety and stability existing problems that antioxidant makes the finished product.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and corresponding lutein ester product of safe, convenient, high purity lutein ester product that product yield is high.
The preparation method who contains the composition of lutein ester of the present invention comprises the steps:
A. under 30～70 ℃ of conditions, marigold extractum is dissolved in mixed solvent A, adds sorbent material to stir 0.5～5 hour, filter, collect filtrate;
B. the filtrate with step a is cooled to 20～28 ℃, keeps after 0.5～4 hour, then is cooled to 5～18 ℃ and kept 0.5～4 hour, filters to get filter cake I;
C. under 30～70 ℃ of conditions, dissolving filter cake I stirs and is cooled to 10～28 ℃ and kept 0.5～5 hour after 0.5～5 hour in mixed solvent A, filters to get filter cake II;
D. use C 1-3Alcohol washing filter cake II then add antioxidant, then drying is removed residual C 1-3Alcohol obtains containing the composition of lutein ester;
Wherein said mixed solvent A is ritalin, vinyl acetic monomer, n-propyl acetate or N-BUTYL ACETATE and C 1-3The mixed solvent of alcohol.
Marigold extractum of the present invention is the medicinal extract that the marigold flower grain obtains through organic solvent extraction, and wherein total ester quality percentage composition should be 18～35%.The normal organic solvent that uses is propane or No. six solvents (GB16629-1996 6 solvent for extraction).
C of the present invention 1-3Alcohol refers to methyl alcohol, ethanol, propyl alcohol or Virahol.
In the preferred technical scheme of this law, the mixed solvent A in described method is the binary mixed solvent of ritalin/methyl alcohol, vinyl acetic monomer/ethanol or n-propyl acetate/Virahol.The most preferably mixed solvent of ritalin/methyl alcohol or vinyl acetic monomer/ethanol.
In the method for the invention described above, in described mixed solvent A, the mass ratio of ester and alcohol is 2: 8～9: 1.
In another optimal technical scheme of the present invention, the mass ratio of the marigold extractum in described step a and mixed solvent A is 1: 0.5～1: 20, preferred 1: 0.5～1: 15, and most preferably 1: 1～1: 10; In step c, the mass ratio of filter cake I and mixed solvent A is 1: 0.5～20, preferred 1: 0.5～1: 15, and most preferably 1: 1～1: 10.
In another optimal technical scheme of the present invention, the rate of temperature fall of described step b and step c is 5～20 ℃/hour, more preferably 5～15 ℃/hour.
In an optimal technical scheme more of the present invention, the alcohol in described steps d is ethanol or Virahol, preferred alcohol; The consumption of alcohol is 3～30 times of filter cake II quality, preferred 3～20 times, and most preferably 4～15 times.
In arbitrary technical scheme of the invention described above, the sorbent material of addressing is selected from the mixture that gac, carclazyte, diatomite, EDTA, EDETATE DISODIUM and above-mentioned two or more sorbent material form with arbitrary proportion; Preferably with 1～3 kind of mixture that forms with arbitrary proportion in gac, carclazyte, diatomite; Most preferably gac, diatomite or the mixture that both forms with arbitrary proportion.Wherein said gac is take shell and wood chip as raw material, through charing, activation, refining processing; Diatomite is mainly that the diatom test more than 90% forms.
In arbitrary technical scheme of the invention described above, the antioxidant in described steps d is selected from the mixture that vitamin-E, sodium ascorbate, sodium isoascorbate, Vc cetylate, tea-polyphenol and above-mentioned two or more antioxidant mix with arbitrary proportion; The mixture that preferred vitamin E, sodium isoascorbate, Vc cetylate or tea-polyphenol and above-mentioned two or more antioxidant mix with arbitrary proportion; Most preferably vitamin-E, Vc cetylate or the mixture that both mixes with arbitrary proportion.
In the further optimal technical scheme of the present invention, in described steps d, drying temperature is 30～70 ℃, be dried to molten residual≤1ppm.
Another preferred technical scheme of the present invention is omnidistance N in whole preparation process 2The gas protection.
The purpose of another aspect of the present invention is to provide the composition that contains lutein ester by the aforesaid method preparation.
Use aforesaid method of the present invention preparation to contain the composition of lutein ester, whole simple for process, be easy to industrialization, all operations all carries out at low temperatures, has guaranteed to the full extent the stability of product.The products obtained therefrom yield is high, and weight yield can reach more than 25%, and the total ester content that can also guarantee product when guaranteeing yield is greater than 70%, and trans-lutein content has promoted the biological activity when product uses greatly up to 90～93%.
Selected sorbent material can remove heavy metal and pesticide remnant residual in marigold extractum effectively in addition, and mixed solvent also has the effect of the objectionable impurities of removing, thereby has guaranteed the high-quality of the lutein ester product that finally obtains.Add antioxidant after low-carbon alcohol kind solvent washing leaching cake, can prevent that the lutein ester product is oxidized in drying course, experimental results show that to add appropriate antioxidant in the lutein ester product, can guarantee it under room temperature vacuum packaging condition, never degenerate in 3 years.And solvent for use of the present invention is food grade solvent, and the product of preparing meets food sanitation safe.
Embodiment
The gac that adopts in the present invention meets GB/T 13803.4-1999 standard; Carclazyte meets the GB25571-2010 standard, and diatomite meets GB 24265-2009 standard.
The present invention uses disclosed method measuring and calculating lutein ester total ester content in JP 2003201497 (A); Content and the composition of alltrans xenthophylls and alltrans zeaxanthin in use AOAC Offical Method 970.64 (Carotenes and Xanthophylls in Dried PlantMaterials and Mixed Feeds) mensuration lutein ester.
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Wherein said " total ester content " is the lutein ester total ester content, according to the mass percent meter.
Embodiment 1
Take the marigold extractum that the 100g total ester content is 28wt%, 1100g mixes with ritalin/methyl alcohol (weight ratio is 2: 8), adds 7g diatomite to filter after 3.5 hours in 60 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I is kept 3h after 1h is cooled to 27 ℃, then filtration obtains filter cake I after 1h is cooled to 9 ℃ of maintenance 4h.
Ritalin/methyl alcohol (weight ratio is 2: 8) the dissolving filter cake I that adds 4 times of filter cake I quality under 55 ℃, filter after slow cooling to 11 ℃ maintenance 3.5h after heated and stirred 5h and obtain filter cake II, the methyl alcohol agitator treating filter cake II that adds 12 times of its quality, add 1.2g tea-polyphenol and 0.6g vitamins C in solid after methanol wash, dry 5h under 45 ℃, obtain product 27g, the quality percentage composition that contains after testing lutein ester is 67%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=91: 5.
Embodiment 2
The marigold extractum that takes the 100g total ester content and be 27wt% is mixed with ritalin/ethanol (weight ratio is 2.5: 7.5) 1800g, adds 6.5gEDTA and 0.5g carclazyte to filter after 3 hours in 48 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 1h after 1h is cooled to 23.5 ℃, then filtration obtains filter cake I after 1h is cooled to 13 ℃ of maintenance 2.5h.
Ritalin/Virahol (weight ratio is 5: 5) the dissolving filter cake I that adds 0.5 times of filter cake I quality under 60 ℃, filter after slow cooling to 11.5 ℃ maintenance 4h after heated and stirred 2h and obtain filter cake II, the methyl alcohol agitator treating filter cake II that adds 8 times of its quality, add 0.5g vitamin-E and 0.3g Vc cetylate in solid after methanol wash, dry 17h under 32 ℃, obtain product 26g, the quality percentage composition that contains after testing lutein ester is 66%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=91: 6.
Embodiment 3
The marigold extractum that takes the 100g total ester content and be 26wt% is mixed with vinyl acetic monomer/methyl alcohol (weight ratio is 2: 8) 1350g, adds the 15g carclazyte to filter after 4.5 hours in 32 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 3h after 1h is cooled to 26.5 ℃, then filtration obtains filter cake I after 1h is cooled to 8.5 ℃ of maintenance 1.5h.
Vinyl acetic monomer/Virahol (weight ratio is 6: 4) the dissolving filter cake I that adds 20 times of filter cake I quality under 65 ℃, filter after slow cooling to 28 ℃ maintenance 1h after heated and stirred 0.5h and obtain filter cake II, the Virahol agitator treating filter cake II that adds 30 times of its quality, add the 1.5g vitamin-E in solid after washed with isopropyl alcohol, dry 24h under 30 ℃, obtain product 20g, the quality percentage composition that contains after testing lutein ester is 70%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=91: 6.
Embodiment 4
The marigold extractum that takes the 100g total ester content and be 28wt% is mixed with n-propyl acetate/propyl alcohol (weight ratio is 3: 7) 800g, adds 3g gac and 2g EDTA to filter after 3 hours in 40 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 4h after 40min is cooled to 28 ℃, then filtration obtains filter cake I after 40min is cooled to 18 ℃ of maintenance 4h.
N-propyl acetate/propyl alcohol (weight ratio is 3: 7) the dissolving filter cake I that adds 8 times of filter cake I quality under 60 ℃, filter after slow cooling to 10 ℃ maintenance 0.5h after heated and stirred 2.5h and obtain filter cake II, the Virahol agitator treating filter cake II that adds 10 times of its quality, add 1.2g Ascorbyl Palmitate and 0.6g sodium isoascorbate in solid after washed with isopropyl alcohol, dry 1h under 50 ℃, obtain product 24g, the quality percentage composition that contains after testing lutein ester is 71%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=90: 5.
Embodiment 5
The marigold extractum that takes the 100g total ester content and be 28wt% is mixed with vinyl acetic monomer/ethanol (weight ratio is 3: 7) 1000g, adds 7g diatomite and 1g carclazyte to filter after 5 hours in 30 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 4h after 40min is cooled to 20 ℃, then filtration obtains filter cake I after 40min is cooled to 11 ℃ of maintenance 4h.
Vinyl acetic monomer/ethanol (weight ratio is 3: 7) the dissolving filter cake I that adds 1 times of filter cake I quality under 30 ℃, filter after slow cooling to 10 ℃ maintenance 0.5h after heated and stirred 5h and obtain filter cake II, the Virahol agitator treating filter cake II that adds 3 times of its quality, add the 1g sodium isoascorbate in solid after washed with isopropyl alcohol, dry 3h under 70 ℃, obtain product 26g, the quality percentage composition that contains after testing lutein ester is 68%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=92: 6.
Embodiment 6
The marigold extractum that takes the 100g total ester content and be 26wt% is mixed with n-propyl acetate/Virahol (weight ratio is 3: 7) 2000g, adds 3g carclazyte and 7gEDTA to filter after 4.5 hours in 38 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 4h after 40min is cooled to 27.5 ℃, then filtration obtains filter cake I after 40min is cooled to 6.5 ℃ of maintenance 3h.
N-propyl acetate/Virahol (weight ratio is 3: 7) the dissolving filter cake I that adds 12 times of filter cake I quality under 60 ℃, filter after slow cooling to 25.5 ℃ maintenance 2.5h after heated and stirred 4.5h and obtain filter cake II, the methyl alcohol agitator treating filter cake II that adds 30 times of its quality, add 0.2g tea-polyphenol and 1g sodium isoascorbate in solid after washed with isopropyl alcohol, dry 10h under 44 ℃, obtain product 22g, the quality percentage composition that contains after testing lutein ester is 70%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=92: 6.
Embodiment 7
The marigold extractum that takes the 100g total ester content and be 27wt% is mixed with N-BUTYL ACETATE/Virahol (weight ratio is 4: 6) 1300g, adds 3gEDTA disodium salt and 4g diatomite to filter after 1 hour in 60 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 2h after 1h is cooled to 26 ℃, then filtration obtains filter cake I after 40min is cooled to 12 ℃ of maintenance 2.5h.
N-BUTYL ACETATE/ethanol (weight ratio is 6: 4) the dissolving filter cake I that adds 1 times of filter cake I quality under 45 ℃, filter after slow cooling to 13 ℃ maintenance 2h after heated and stirred 1.5h and obtain filter cake II, the ethanol agitator treating filter cake II that adds 20 times of its quality, add 0.4g vitamin-E and 1.4g Ascorbyl Palmitate in solid after washing with alcohol, dry 12h under 40 ℃, obtain product 28g, the quality percentage composition that contains after testing lutein ester is 67%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=92: 5.
Embodiment 8
The marigold extractum that takes the 100g total ester content and be 27wt% is mixed with ritalin/methyl alcohol (weight ratio is 4: 6) 100g, adds 2g carclazyte and 2g diatomite to filter after 4 hours in 45 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 0.5h after 40min is cooled to 21 ℃, then filtration obtains filter cake I after 1h is cooled to 7 ℃ of maintenance 1h.
Ritalin/methyl alcohol (weight ratio is 4: 6) the dissolving filter cake I that adds 1 times of filter cake I quality under 55 ℃, filter after slow cooling to 17 ℃ maintenance 5h after heated and stirred 3h and obtain filter cake II, the Virahol agitator treating filter cake II that adds 8 times of its quality, add 0.4g Vc cetylate in solid after washed with isopropyl alcohol, dry 24h under 30 ℃, obtain product 26g, the quality percentage composition that contains after testing lutein ester is 72%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=92: 5.
Embodiment 9
The marigold extractum that takes the 100g total ester content and be 27wt% is mixed with n-propyl acetate/Virahol (weight ratio is 4.5: 5.5) 1600g, adds 1g diatomite and 12g gac to filter after 1.5 hours in 65 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 1.5h after 1h is cooled to 25 ℃, then filtration obtains filter cake I after 1h is cooled to 6 ℃ of maintenance 1h.
N-propyl acetate/Virahol (weight ratio is 4.5: 5.5) the dissolving filter cake I that adds 17 times of filter cake I quality under 30 ℃, filter after slow cooling to 14 ℃ maintenance 3.5h after heated and stirred 4.5h and obtain filter cake II, the Virahol agitator treating filter cake II that adds 8 times of its quality, add 0.5g Vc cetylate and 1g vitamins C in solid after methanol wash, dry 11h under 54 ℃, obtain product 25g, the quality percentage composition that contains after testing lutein ester is 73%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=91: 6.
Embodiment 10
The marigold extractum that takes the 100g total ester content and be 28wt% is mixed with ritalin/ethanol (weight ratio is 5: 5) 1000g, adds the 10g carclazyte to filter after 0.5 hour in 70 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 3h after 1h is cooled to 20 ℃, then filtration obtains filter cake I after 40min is cooled to 10 ℃ of maintenance 1.5h.
Ritalin/ethanol (weight ratio is 5: 5) the dissolving filter cake I that adds 10 times of filter cake I quality under 60 ℃, filter after slow cooling to 22 ℃ maintenance 5h after heated and stirred 2h and obtain filter cake II, the methyl alcohol agitator treating filter cake II that adds 15 times of its quality, add the 0.5g vitamin C sodium salt in solid after methanol wash, dry 4h under 70 ℃, obtain product 26g, the quality percentage composition that contains after testing lutein ester is 74%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=93: 6.
Embodiment 11
The marigold extractum that takes the 100g total ester content and be 28wt% is mixed with ritalin/methyl alcohol (weight ratio is 5: 5) 700g, adds 1g diatomite and 8gEDTA to filter after 0.5 hour in 70 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 3.5h after 1h is cooled to 23 ℃, then filtration obtains filter cake I after 40min is cooled to 13 ℃ of maintenance 2h.
Ritalin/methyl alcohol (weight ratio is 2: 8) the dissolving filter cake I that adds 20 times of filter cake I quality under 70 ℃, filter after slow cooling to 5.5 ℃ maintenance 3.5h after heated and stirred 2h and obtain filter cake II, the methyl alcohol agitator treating filter cake II that adds 4 times of its quality, add 1.2g tea-polyphenol and 0.4g sodium ascorbate salt in solid after methanol wash, dry 1h under 63 ℃, obtain product 27g, the quality percentage composition that contains after testing lutein ester is 68%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=91: 5.
Embodiment 12
The marigold extractum that takes the 100g total ester content and be 28wt% is mixed with n-propyl acetate/Virahol (weight ratio is 5: 5) 700g, adds 2g gac and 4g carclazyte to filter after 2.5 hours in 64 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 3.5h after 1h is cooled to 24.5 ℃, then filtration obtains filter cake I after 1h is cooled to 8 ℃ of maintenance 0.5h.
N-propyl acetate/Virahol (weight ratio is 5: 5) the dissolving filter cake I that adds 1 times of filter cake I quality under 60 ℃, filter after slow cooling to 14.5 ℃ maintenance 2h after heated and stirred 1h and obtain filter cake II, the Virahol agitator treating filter cake II that adds 10 times of its quality, add 0.6g vitamin-E and 0.2g Vc cetylate in solid after washed with isopropyl alcohol, dry 1.5h under 55 ℃, obtain product 25g, the quality percentage composition that contains after testing lutein ester is 70%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=92: 6.
Embodiment 13
The marigold extractum that takes the 100g total ester content and be 28wt% is mixed with vinyl acetic monomer/ethanol (weight ratio is 5: 5) 200g, adds 1g gac and 4g diatomite to filter after 0.5 hour in 60 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 1h after 1h is cooled to 25 ℃, then filtration obtains filter cake I after 40min is cooled to 10 ℃ of maintenance 2h.
Vinyl acetic monomer/ethanol (weight ratio is 5: 5) the dissolving filter cake I that adds 10 times of filter cake I quality under 60 ℃, filter after slow cooling to 25 ℃ maintenance 1h after heated and stirred 1h and obtain filter cake II, the ethanol agitator treating filter cake II that adds 4 times of its quality, add 0.5g vitamin-E and 0.1g Vc cetylate in solid after washing with alcohol, dry 3h under 40 ℃, obtain product 27g, the quality percentage composition that contains after testing lutein ester is 74%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=92: 6.
Embodiment 14
The marigold extractum that takes the 100g total ester content and be 28wt% is mixed with vinyl acetic monomer/Virahol (weight ratio is 6: 4) 650g, adds 5g carclazyte and 8g diatomite to filter after 5 hours in 30 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 0.5h after 40min is cooled to 25 ℃, then filtration obtains filter cake I after 1h is cooled to 5 ℃ of maintenance 0.5h.
N-propyl acetate/Virahol (weight ratio is 3.5: 6.5) the dissolving filter cake I that adds 20 times of filter cake I quality under 58 ℃, filter after slow cooling to 23 ℃ maintenance 1h after heated and stirred 1.5h and obtain filter cake II, the Virahol agitator treating filter cake II that adds 30 times of its quality, add 1.5g Vc cetylate in solid after washed with isopropyl alcohol, dry 10h under 44 ℃, obtain product 21g, the quality percentage composition that contains after testing lutein ester is 67%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=92: 5.
Embodiment 15
The marigold extractum that takes the 100g total ester content and be 26wt% is mixed with vinyl acetic monomer/Virahol (weight ratio is 6: 4) 400g, adds 2g gac and 8g diatomite to filter after 4 hours in 47 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 1.5h after 1h is cooled to 24.5 ℃, then filtration obtains filter cake I after 40min is cooled to 13.5 ℃ of maintenance 3.5h.
N-BUTYL ACETATE/ethanol (weight ratio is 3: 7) the dissolving filter cake I that adds 15 times of filter cake I quality under 59 ℃, filter after slow cooling to 18 ℃ maintenance 3h after heated and stirred 1.5h and obtain filter cake II, the ethanol agitator treating filter cake II that adds 7 times of its quality, add the 1.5g sodium isoascorbate in solid after washing with alcohol, dry 2h under 59 ℃, obtain product 21.5g, the quality percentage composition that contains after testing lutein ester is 71%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=93: 5.
Embodiment 16
The marigold extractum that takes the 100g total ester content and be 26wt% is mixed with ritalin/ethanol (weight ratio is 6: 4) 600g, adds the 8.5gEDTA disodium salt to filter after 2.5 hours in 38 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 4h after 40min is cooled to 20.5 ℃, then filtration obtains filter cake I after 40min is cooled to 12 ℃ of maintenance 3h.
Ritalin/methyl alcohol (weight ratio is 2: 8) the dissolving filter cake I that adds 4 times of filter cake I quality under 55 ℃, filter after slow cooling to 10 ℃ maintenance 3.5h after heated and stirred 5h and obtain filter cake II, the methyl alcohol agitator treating filter cake II that adds 22 times of its quality, add the 1.0g tea-polyphenol in solid after methanol wash, dry 2.5h under 66 ℃, obtain product 27g, the quality percentage composition that contains after testing lutein ester is 67%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=93: 5.
Embodiment 17
The marigold extractum that takes the 100g total ester content and be 26wt% is mixed with vinyl acetic monomer/ethanol (weight ratio is 6: 4) 300g, adds the 5g gac to filter after 2 hours in 50 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 2h after 1h is cooled to 28 ℃, then filtration obtains filter cake I after 1h is cooled to 8 ℃ of maintenance 1.5h.
Vinyl acetic monomer/ethanol (weight ratio is 6: 4) the dissolving filter cake I that adds 1 times of filter cake I quality under 70 ℃, filter after slow cooling to 28 ℃ maintenance 2h after heated and stirred 0.5h and obtain filter cake II, the ethanol agitator treating filter cake II that adds 6 times of its quality, add 0.1g vitamin-E and 0.1g Vc cetylate in solid after washing with alcohol, dry 1h under 50 ℃, obtain product 28g, the quality percentage composition that contains after testing lutein ester is 71%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=92: 6.
Embodiment 18
The marigold extractum that takes the 100g total ester content and be 27wt% is mixed with n-propyl acetate/methyl alcohol (weight ratio is 6.5: 3.5) 1200g, adds 4g gac and 2g Vc cetylate to filter after 1 hour in 66 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 3h after 1h is cooled to 24.5 ℃, then filtration obtains filter cake I after 1h is cooled to 7.5 ℃ of maintenance 2h.
N-BUTYL ACETATE/propyl alcohol (weight ratio is 6.5: 3.5) the dissolving filter cake I that adds 13 times of filter cake I quality under 46 ℃, filter after slow cooling to 12 ℃ maintenance 4.5h after heated and stirred 2h and obtain filter cake II, the methyl alcohol agitator treating filter cake II that adds 14 times of its quality, add the 2g Ascorbyl Palmitate in solid after methanol wash, dry 0.5h under 67 ℃, obtain product 22g, the quality percentage composition that contains after testing lutein ester is 69%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=91: 5.
Embodiment 19
The marigold extractum that takes the 100g total ester content and be 27wt% is mixed with ritalin/methyl alcohol (weight ratio is 7: 3) 1500g, adds 13g diatomite to filter after 2 hours in 65 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 1.5h after 1h is cooled to 25 ℃, then filtration obtains filter cake I after 40min is cooled to 18 ℃ of maintenance 2h.
Ritalin/methyl alcohol (weight ratio is 7: 3) the dissolving filter cake I that adds 15 times of filter cake I quality under 48 ℃, filter after slow cooling to 23 ℃ maintenance 4h after heated and stirred 2.5h and obtain filter cake II, the methyl alcohol agitator treating filter cake II that adds 20 times of its quality, add 0.4g Vc cetylate in solid after methanol wash, dry 24h under 30 ℃, obtain product 23g, the quality percentage composition that contains after testing lutein ester is 70%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=92: 5.
Embodiment 20
The marigold extractum that takes the 100g total ester content and be 26wt% is mixed with vinyl acetic monomer/ethanol (weight ratio is 8: 2) 500g, adds the 11g carclazyte to filter after 1 hour in 70 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 3h after 1.5h is cooled to 20 ℃, then filtration obtains filter cake I after 1h is cooled to 5 ℃ of maintenance 3h.
Vinyl acetic monomer/ethanol (weight ratio is 8: 2) the dissolving filter cake I that adds 5 times of filter cake I quality under 50 ℃, filter after slow cooling to 15 ℃ maintenance 2h after heated and stirred 3h and obtain filter cake II, the ethanol agitator treating filter cake II that adds 15 times of its quality, add in solid after washing with alcohol under 30 ℃ of 0.5g vitamin-Es and dry 16h, obtain product 26g, the quality percentage composition that contains after testing lutein ester is 72%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=92: 5.
Embodiment 21
The marigold extractum that takes the 100g total ester content and be 27wt% is mixed with n-propyl acetate/ethanol (weight ratio is 8: 2) 900g, adds the 10g EDETATE DISODIUM to filter after 2.5 hours in 55 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 2.5h after 1h is cooled to 22.5 ℃, then filtration obtains filter cake I after 1h is cooled to 9.5 ℃ of maintenance 0.5h.
N-propyl acetate/Virahol (weight ratio is 5: 5) the dissolving filter cake I that adds 8 times of filter cake I quality under 60 ℃, filter after slow cooling to 18 ℃ maintenance 5h after heated and stirred 2.5h and obtain filter cake II, the ethanol agitator treating filter cake II that adds 20 times of its quality, add 1.4g vitamin-E and 1.6g sodium isoascorbate in solid after washing with alcohol, dry 14h under 33 ℃, obtain product 25g, the quality percentage composition that contains after testing lutein ester is 66%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=92: 5.
Embodiment 22
The marigold extractum that takes the 100g total ester content and be 25wt% is mixed with N-BUTYL ACETATE/methyl alcohol (weight ratio is 8: 2) 100g, adds 12g diatomite to filter after 4 hours in 50 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 4h after 1h is cooled to 23 ℃, then filtration obtains filter cake I after 0.5h is cooled to 16 ℃ of maintenance 4h.
N-BUTYL ACETATE/methyl alcohol (weight ratio is 8: 2) the dissolving filter cake I that adds 6 times of filter cake I quality under 30 ℃, filter after slow cooling to 27 ℃ maintenance 3.5h after heated and stirred 5h and obtain filter cake II, the propyl alcohol agitator treating filter cake II that adds 3 times of its quality, add the 0.8g vitamins C in solid after the propyl alcohol washing, dry 10h under 30 ℃, obtain product 26g, the quality percentage composition that contains after testing lutein ester is 67%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=91: 5.
Embodiment 23
((weight ratio is 9: 1) 1000g mixes, and adds 7g diatomite and 0.5g carclazyte to filter after 5 hours in 30 ℃ of lower heated and stirred, obtains mother liquor I with n-propyl acetate/Virahol to take the 100g total ester content and be the marigold extractum of 27wt%.Mother liquor I slow cooling is kept 4h after 0.5h is cooled to 20 ℃, then filtration obtains filter cake I after 0.5h is cooled to 11 ℃ of maintenance 3h.
Vinyl acetic monomer/ethanol (weight ratio is 3: 7) the dissolving filter cake I that adds 1 times of filter cake I quality under 43 ℃, filter after slow cooling to 12.5 ℃ maintenance 1.5h after heated and stirred 5h and obtain filter cake II, the Virahol agitator treating filter cake II that adds 3 times of its quality, add the 1.5g sodium isoascorbate in solid after washed with isopropyl alcohol, dry 3h under 70 ℃, obtain product 26g, the quality percentage composition that contains after testing lutein ester is 69%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=92: 6.
Embodiment 24
The marigold extractum that takes the 100g total ester content and be 26wt% is mixed with ritalin/methyl alcohol (weight ratio is 9: 1) 50g, adds the 8g EDETATE DISODIUM to filter after 3 hours in 35 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 1.5h after 40min is cooled to 21.5 ℃, then filtration obtains filter cake I after 0.5h is cooled to 18 ℃ of maintenance 2h.
Ritalin/methyl alcohol (weight ratio is 7: 3) the dissolving filter cake I that adds 10 times of filter cake I quality under 48 ℃, filter after slow cooling to 23 ℃ maintenance 4h after heated and stirred 2.5h and obtain filter cake II, the ethanol agitator treating filter cake II that adds 30 times of its quality, add the 0.8g tea-polyphenol in solid after washing with alcohol, dry 14h under 35 ℃, obtain product 22g, the quality percentage composition that contains after testing lutein ester is 70%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=92: 5.
Embodiment 25
The marigold extractum that takes the 100g total ester content and be 26wt% is mixed with n-propyl acetate/Virahol (weight ratio is 9: 1) 100g, adds 2g gac and 4gEDTA disodium salt to filter after 2 hours in 58 ℃ of lower heated and stirred, obtains mother liquor I.Mother liquor I slow cooling is kept 4h after 1h is cooled to 23 ℃, then filtration obtains filter cake I after 1h is cooled to 6 ℃ of maintenance 0.5h.
N-propyl acetate/Virahol (weight ratio is 9: 1) the dissolving filter cake I that adds 0.5 times of filter cake I quality under 60 ℃, filter after slow cooling to 10.5 ℃ maintenance 1.5h after heated and stirred 1h and obtain filter cake II, the ethanol agitator treating filter cake II that adds 10 times of its quality, add 0.6g vitamin-E and 0.2g tea-polyphenol in solid after washing with alcohol, dry 5h under 42 ℃, obtain product 26g, the quality percentage composition that contains after testing lutein ester is 68%, wherein alltrans xenthophylls: zeaxanthin (mol ratio)=91: 5.

Claims (7)

1. contain the preparation method of the composition of lutein ester, comprise the steps:
A. under 30～70 ℃ of conditions, marigold extractum is dissolved in mixed solvent A, adds sorbent material to stir 0.5～5 hour, filter, collect filtrate; The mass ratio of described marigold extractum and mixed solvent A is 1:0.5～1:20;
B. the filtrate of step a is cooled to 20～28 ℃ with the speed of 5～20 ℃/hour, keeps after 0.5～4 hour, then be cooled to 5～18 ℃ and kept 0.5～4 hour with the speed of 5～20 ℃/hour, filter to get filter cake I;
C. under 30～70 ℃ of conditions, dissolving filter cake I stirs after 0.5～5 hour with the speed of 5～20 ℃/hour and is cooled to 10～28 ℃ and kept 0.5～5 hour in mixed solvent A, filters to get the filter cake II; The mass ratio of described filter cake I and mixed solvent A is 1:0.5～20;
D. use C 1-3Alcohol washing filter cake II then add antioxidant, then drying is removed residual C 1-3Alcohol obtains containing the composition of lutein ester; Described C 1-3Alcohol is ethanol or Virahol;
Wherein said mixed solvent A is the binary mixed solvent of methyl acetate and methanol, vinyl acetic monomer-ethanol or n-propyl acetate-Virahol; Wherein the mass ratio of ester and alcohol is 2:8～9:1.
2. method claimed in claim 1 is characterized in that marigold extractum in described step a and the mass ratio of mixed solvent A are 1:1～1:10; In step c, the mass ratio of filter cake I and mixed solvent A is 1:1～1:10.
3. method claimed in claim 1, is characterized in that C in described steps d 1-3The consumption of alcohol is 3～30 times of filter cake II quality.
4. method claimed in claim 1, is characterized in that described sorbent material is selected from the mixture that gac, carclazyte, diatomite, EDTA, EDETATE DISODIUM and above-mentioned two or more sorbent material form with arbitrary proportion.
5. method claimed in claim 1, is characterized in that the antioxidant in described steps d is selected from the mixture that vitamin-E, sodium ascorbate, sodium isoascorbate, Vc cetylate, tea-polyphenol and above-mentioned two or more antioxidant mix with arbitrary proportion.
6. method claimed in claim 1 is characterized in that in described steps d 30～70 ℃ of drying temperatures, be dried to molten residual≤1ppm.
7. method claimed in claim 1, is characterized in that omnidistance N in whole preparation process 2The gas protection.
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CN102659653B (en) * 2012-05-05 2013-11-06 邯郸市中进天然色素有限公司 Purification method from lutein extractive to high-purity lutein ester
CN103130699B (en) * 2013-03-11 2015-07-22 大连医诺生物有限公司 Food-grade high-content lutein ester and preparation method thereof
CN103626686A (en) * 2013-12-09 2014-03-12 新疆特瑞生物科技有限公司 Method for extracting lutein ester from marigold
CN103992256B (en) * 2014-05-17 2016-09-07 昆明涞章医药科技有限公司 A kind of method preparing high-purity lutein ester from pot marigold
CN107987001B (en) * 2017-12-12 2021-02-02 广州立达尔生物科技股份有限公司 Method for rapidly preparing high-content natural lutein ester
US20220220059A1 (en) 2021-01-14 2022-07-14 Kemin Industries, Inc. Process for crystallization of high purity lutein esters from marigold extracts

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CN101891664A (en) * 2010-07-21 2010-11-24 云南瑞宝生物科技有限公司 Method for purifying lutein esters

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