CN1309693C - Lutein crystal preparing process from marigold flower - Google Patents
Lutein crystal preparing process from marigold flower Download PDFInfo
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- CN1309693C CN1309693C CNB021108064A CN02110806A CN1309693C CN 1309693 C CN1309693 C CN 1309693C CN B021108064 A CNB021108064 A CN B021108064A CN 02110806 A CN02110806 A CN 02110806A CN 1309693 C CN1309693 C CN 1309693C
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Abstract
The present invention relates to a process for preparing lutein crystals from marigold flower, which comprises: firstly, a non-polar solvent is used for extracting lutein ester from marigold flower under the condition of heating; then, under the condition of stirring and heating, the concentrated solution of lutein ester is saponified with alkaline solution, and after being diluted with deionized water, saponification reaction products are separated, washed and dried in vacuum; finally, obtained lutein crystals are crystallized in a three-component solvent of tetrahydrofuran, deionized water and n-hexane or petroleum ether while being slowly stirred, and the procedures of sucking filtration, washing and vacuum drying are carried out. The present invention has the advantages of low toxicity, low consumption and easy recovery of the used solvent, easy separation, simple technological operation, easy industrialization, high extraction yield of 72% to 86%, and high product purity of 95% to 98%. The product produced by using the method of the present invention can be widely used as a fodder colorant, a food colorant, a medicinal health protection product, etc.
Description
Technical field
Patent of the present invention relates to a kind of method for preparing lutein crystal from marigold flower.
Background technology
Xenthophylls (Lutein) is a kind of in the carotenoid, in flowers such as deep green leaf vegetables such as wild cabbage, kale and spinach and Potmarigold Calendula, Flower of Aztec Marigold very high content is arranged.Xenthophylls is one of the most effective hyperchromic additive in the carotenoid, is used for appearance luster and interior quality that animal and fowl fodder can improve animal products; Natural carotenol still is a kind of oxidation inhibitor of excellent performance, as foodstuff additive, because of a series of diseases that organ senescence causes good effect is arranged to preventing human body, as the visual deterioration that can prevent senile eyeball macula retinae to degenerate to cause with blind.
With the marigold flower is that raw material extracts xenthophylls, domestic prior art only limits to produce pasty state liquid and paste resin, developed the method for extracting lutein resin from marigold flower as Foodstuff Inst. of Science and Tech. Education Development Co., Qingdao Univ. (C, this method is used Petroleum ether extraction with the marigold flower of plucking after fermentation, drying, pulverizing, extracting solution gets work in-process through heating evaporation, again through deodorization and the partly-hydrolysed lutein resin finished product that gets.Extract xenthophylls in this way, extraction yield is 11.5%～14.5%, and product purity is 11%～13.5%.External existing bibliographical information from marigold flower extraction, separation, purification lutein crystal, but described technology exists the lutein crystal separation difficulty if apply to produce actual time, problems such as the organic solvent usage quantity is big, recovery difficulty.As: U.S. Pat 5382714, consumption of organic solvent is big during saponification, and the xenthophylls separating difficulty is big, and product content is low, and recrystallization uses deleterious methylene chloride two combination solvents, is unfavorable for the application of product in food and medicine; US 5648564, with 45% alkali propylene glycol solution saponification, because propylene glycol viscosity height, thereby have the problem of separating difficulty equally, and the extremely difficult recycling of the propylene glycol in the waste liquid, easily environment is polluted; And US6262284 uses tetrahydrofuran (THF) and the alkali alcoholic solution at room temperature extracts simultaneously, saponification, reclaim organic solvent at last, but the organic solvent amount is excessive, energy and solvent consumption are too big, again because under alkaline condition, esterification easily takes place with alcohol in higher fatty acid salt, generates the high-grade aliphatic ester micelle and separates out with xenthophylls, so lutein crystal also is difficult to separate and purify.
Summary of the invention
The objective of the invention is defective at above-mentioned prior art existence, provide that a kind of solvent for use toxicity is low, consumption is little and be easy to and reclaim, sepn process is easy, very easily realizes industrialization, and extracts yield height, the method for preparing lutein crystal from marigold flower that product purity is high.
For realizing this purpose, technical scheme of the present invention is: at first extract lutein ester with non-polar solvent under heating condition from marigold flower; Vacuum recovery part non-polar solvent forms the strong solution of lutein ester then; Under stirring and heating condition, the lutein ester strong solution is carried out saponification again with alkaline solution; With deionized water the saponification reaction product is diluted after the saponification reaction; Then from diluent, separate, collect lutein crystal; Then extremely neutral with warm deionized water washing gained lutein crystal, vacuum-drying then; After this with the gained lutein crystal under slowly stirring in tetrahydrofuran (THF)/deionized water/normal hexane or sherwood oil three combination solvents recrystallization; Suction filtration more subsequently, washing, vacuum-drying.
In the present invention, described marigold flower is through pretreated, and the fresh Flos Tagetis Erectae of harvesting becomes dried marigold flower particle through fermentation, dehydration, drying, pulverizing and granulation, as the raw material of preparation lutein crystal.
Described non-polar solvent is C
6～C
8Naphthenic hydrocarbon, straight-chain paraffin, branched paraffin, aromatic hydrocarbon or ethers.The temperature that heats during extraction is 45 ℃～65 ℃.Extract operation and should carry out several.
To extract the gained extracting solution for several times and merge, vacuum recovery part non-polar solvent is to form the lutein ester strong solution, and the concentration of lutein ester strong solution should be controlled in 2.0%～8.0% scope.
Above-mentioned lutein ester strong solution contains lutein ester, anthocyanidin, chlorophyll and derivative and water miscible flavonoid etc.The lutein ester strong solution is after saponification reaction, anthocyanidin wherein, chlorophyll and derivative thereof and flavonoid are soluble in the deionized water, the lutein ester major part is saponified into free xenthophylls and higher fatty acid salt, higher fatty acid salt is dissolved in the hot water, wherein also have sub-fraction not saponification high-grade aliphatic ester and oil soluble preferably other carotenoid still be distributed in the non-polar solvent.The present invention carries out saponification with alkaline solution to above-mentioned lutein ester strong solution under stirring and heating condition, described alkaline solution is meant the polar solvent of alkali metal hydroxide or organic amine, and its solvent is a deionized water, and the concentration of alkaline solution is 2.0%～45.0%.For helping the carrying out of saponification reaction, the volume ratio of alkaline solution that adds in the lutein ester strong solution and lutein ester strong solution is 0.5～3.0, and the saponification reaction temperature is 50 ℃～80 ℃, in 3 hours～10 hours reaction times, is at least 3 hours.After utilization thin-layer chromatography method shows that saponification reaction fully, leave standstill cooling.
With 60 ℃～70 ℃ deionized waters reaction product is diluted after the saponification reaction, the volume of used deionized water is 1.0～4.0 times of the preceding alkaline solution volume that is added of saponification reaction.
The dilution back adopts modes such as vacuum filtration or centrifugation to collect lutein crystal; Be that 40 ℃～70 ℃ deionized water washing is collected the gained lutein crystal to neutral with temperature again; Under room temperature or 25 ℃～40 ℃ conditions lutein crystal is carried out vacuum-drying then, be 24 hours～72 hours time of drying.
Then the gained lutein crystal is carried out recrystallization, the xenthophylls recrystallization carries out under slowly stirring, consisting of of used tetrahydrofuran (THF)/deionized water/normal hexane or sherwood oil three combination solvents: tetrahydrofuran (THF) accounts for 30%～60%, deionized water accounts for 20%～50%, and normal hexane or sherwood oil account for 10%～40%; Slowly stir after 0.5 hour～2 hours, quiet heavy; Suction filtration; Again with the washing of 95% edible ethanol, to remove impurity such as residual normal hexane, water and plant sterol; Vacuum-drying lutein crystal under room temperature or 25 ℃～40 ℃ conditions, be 24 hours～72 hours time of drying.Lutein content reaches more than 97%.
Of the present inventionly prepare that the method solvent for use toxicity of lutein crystal is low, consumption is little and be easy to reclaim from marigold flower, separating difficulty is low, and technological operation is easy, easily realize industrialization, extract the yield height, can reach 72%～86%, the product purity height can reach 95%～98%.The product of being produced by the method for the invention can be widely used as the hyperchromic additive of feed, food colorant and Medicines and Health Product etc.
Embodiment
Embodiment 1:
Extraction, saponification, separation, washing, drying: dried marigold flower particle 2kg, normal hexane 2L, 60 ℃ of following continuous extraction 5～6 times, united extraction liquid vacuum reclaims normal hexane to 500ml～600ml volume; After being warming up to 56 ℃, under agitation, add sodium hydroxide 40g, the weight ratio of sodium hydroxide and water is 1: 5; Controlled temperature stirs saponification 3 hours～10 hours at 50 ℃～60 ℃, after utilization thin-layer chromatography method shows that saponification reaction fully, leaves standstill cooling; With the 100ml temperature is 60 ℃ of deionized water dilution saponification reaction products, carries out centrifugation again; The gained lutein crystal washs to elutant with 70 ℃ deionized water and is neutral; Drying is 72 hours under vacuum and room temperature, obtains the 35.5g lutein crystal, and content is 83%, and the total extraction yield of xenthophylls is 85.2%.
Recrystallization: lutein crystal (10g, 83%) is dissolved in the 200ml tetrahydrofuran (THF), slowly drips the 300ml deionized water while stirring in tetrahydrofuran solution, slowly adds the 100ml normal hexane after 5 minutes, slowly stirs 30 minutes after dropwising again, and is quiet heavy; Suction filtration; Wash with 95% edible ethanol 100ml again; Drying is 24 hours under vacuum and room temperature, obtains lutein crystal 6.5g, and content reaches 97.5%.
Embodiment 2:
Extraction, saponification, separation, washing, drying: dried marigold flower pellets 2kg, sherwood oil 2L, 60 ℃ of following continuous extraction 5～6 times, united extraction liquid vacuum reclaims sherwood oil to 500ml～600ml volume; After being warming up to 56 ℃, under agitation, add sodium hydroxide 60g, the weight ratio of sodium hydroxide and water is 1: 5, and controlled temperature stirs saponification 3 hours～10 hours at 50 ℃～60 ℃, after utilization thin-layer chromatography method shows that saponification reaction fully, leaves standstill cooling; With the 100ml temperature is 60 ℃ of deionized water dilution saponification reaction products, carries out centrifugation again; The lutein crystal of collecting washs to elutant with 70 ℃ deionized water and is neutral; Under vacuum and room temperature dry 72 hours, obtain 37.3g content and be 75.6% lutein crystal, the total extraction yield of xenthophylls is 75.10%.
Recrystallization: lutein crystal (10g, 75.6%) is dissolved in the 200ml tetrahydrofuran (THF), slowly drips the 300ml deionized water while stirring in tetrahydrofuran solution, slowly adds the 100ml normal hexane after 5 minutes, slowly stirs 30 minutes after dropwising again, and is quiet heavy; Suction filtration; Wash with 95% edible ethanol 100ml again; Drying is 24 hours under vacuum and room temperature, obtains lutein crystal 6.5g, and content reaches 97.2%.
Claims (11)
1. one kind prepares the method for lutein crystal from marigold flower, it is characterized in that it comprises the following steps:
(a) adopt non-polar solvent under heating condition, from marigold flower, to extract lutein ester;
(b) vacuum recovery part non-polar solvent forms the strong solution of lutein ester, and the concentration of the lutein ester strong solution of formation is 2.0%～8.0%;
(c) under stirring and heating condition, the lutein ester strong solution is carried out saponification with alkaline solution;
(d) with deionized water the saponification reaction product is diluted;
(e) from diluent, separate, collect lutein crystal;
(f) wash (e) gained lutein crystal to neutrality with warm deionized water, vacuum-drying;
(g) (f) gained lutein crystal under slowly stirring in tetrahydrofuran (THF)/deionized water/normal hexane or sherwood oil three combination solvents recrystallization;
(h) suction filtration;
(i) with edible ethanol washing (h) gained lutein crystal, vacuum-drying then.
2. the method for claim 1, wherein non-polar solvent is C
6～C
8Naphthenic hydrocarbon, straight-chain paraffin, branched paraffin, aromatic hydrocarbon or ethers.
3. the temperature of heating is 45 ℃～65 ℃ when the method for claim 1, wherein extracting.
4. the method for claim 1, wherein alkaline solution is meant the polar solvent of alkali metal hydroxide or organic amine, and its solvent is a deionized water, and the concentration of alkaline solution is 2.0%～45.0%
5. as claim 1 or 4 described methods, wherein, the volume ratio of alkaline solution that adds in the lutein ester strong solution and lutein ester strong solution is 0.5～3.0.
6. the method for claim 1, wherein the saponification reaction temperature is 50 ℃～80 ℃, and the reaction times was at least 3 hours.
The method of claim 1, wherein after the saponification reaction volume of the used deionized water of diluting reaction product be 1.0～4.0 times of the alkaline solution volume that added before the saponification reaction.
8. the mode of the method for claim 1, wherein separating, collecting lutein crystal is vacuum filtration or centrifugation.
9. the temperature of the method for claim 1, wherein washing the used deionized water of lutein crystal is 40 ℃～70 ℃.
10. the method for claim 1, wherein the temperature of vacuum-drying lutein crystal is 25 ℃～40 ℃, and be 24 hours～72 hours time of drying.
11. the method for claim 1, wherein used three combination solvents of xenthophylls recrystallization, tetrahydrofuran (THF) accounts for 30%～60%, and deionized water accounts for 20%～50%, and normal hexane or sherwood oil account for 10%～40%.
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| CNB021108064A CN1309693C (en) | 2002-02-05 | 2002-02-05 | Lutein crystal preparing process from marigold flower |
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| CNB021108064A CN1309693C (en) | 2002-02-05 | 2002-02-05 | Lutein crystal preparing process from marigold flower |
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| CN1436774A CN1436774A (en) | 2003-08-20 |
| CN1309693C true CN1309693C (en) | 2007-04-11 |
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| CNB021108064A Expired - Lifetime CN1309693C (en) | 2002-02-05 | 2002-02-05 | Lutein crystal preparing process from marigold flower |
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Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1332947C (en) * | 2005-08-03 | 2007-08-22 | 浙江医药股份有限公司新昌制药厂 | Method for separating and purifying lutein crystal from vegetable oleoresin |
| CN101130512B (en) * | 2007-08-31 | 2010-08-25 | 陕西天润植物化工有限公司 | Method for producing xanthophyll |
| CN101429146B (en) * | 2007-11-08 | 2011-11-16 | 宁波绿之健药业有限公司 | High purity xanthophyll crystal produced with marigold petal and producing method thereof |
| CN101402597A (en) * | 2008-10-31 | 2009-04-08 | 南京泛成生物化工有限公司 | Xanthophyll extraction process |
| CN101434568B (en) * | 2008-11-19 | 2012-05-30 | 黑龙江省嘉宝生物技术开发有限公司 | A method for preparing high content xanthophyll crystal from calendula officinalis extract |
| CN101514177B (en) * | 2009-03-13 | 2013-04-03 | 湖北丽生堂生物科技有限公司 | Method for extracting lutein from marigold particles |
| CN101838229B (en) * | 2009-03-19 | 2014-05-14 | 华北制药集团新药研究开发有限责任公司 | Method for separating and purifying all-trans xanthophyl powder |
| US8247615B2 (en) | 2010-05-14 | 2012-08-21 | Kalamazoo Holdings, Inc. | Process of converting esterified xanthophylls from Capsicum to non-esterified xanthophylls in high yields and purities |
| WO2010138210A1 (en) | 2009-05-29 | 2010-12-02 | Kalamazoo Holdings, Inc. | Methods of saponifying xanthophyll esters and isolating xanthophylls |
| CN101774955A (en) * | 2009-12-08 | 2010-07-14 | 江苏省农业科学院 | Method for preparing high-content trans-lutein crystals from dried marigold flower pellets |
| CN101955456A (en) * | 2010-10-14 | 2011-01-26 | 曲靖博浩生物科技股份有限公司 | Method for preparing high purity xanthophyll crystal |
| CN102090511B (en) * | 2011-01-07 | 2012-07-04 | 福州金佰慧生物技术有限公司 | Feed additive containing natural lutein and preparation method thereof |
| US8921615B2 (en) * | 2011-12-31 | 2014-12-30 | Chenguang Biotech Group Co. Ltd. | Process for preparing xanthophyll crystal |
| CN102757373B (en) * | 2012-07-31 | 2014-03-19 | 沈阳天峰生物制药有限公司 | Method for preparing high-purity lutein ester from marigold flower particles |
| 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 |
| CN103193693A (en) * | 2013-04-26 | 2013-07-10 | 辽宁省农业科学院食品与加工研究所 | Preparation process of marigold lutein |
| CN103588690A (en) * | 2013-11-12 | 2014-02-19 | 西安绿森生物科技有限公司 | Process for extracting xanthophyll from Tagetes erecta |
| CN104387307B (en) * | 2014-11-18 | 2016-02-03 | 晨光生物科技集团股份有限公司 | The minimizing technology of ethoxyquinoline in a kind of lutein extract |
| CN105601552A (en) * | 2016-03-18 | 2016-05-25 | 常州市蓝勖化工有限公司 | Method for preparing high-purity lutein crystals by biological process |
| CN106565575A (en) * | 2016-10-24 | 2017-04-19 | 晨光生物科技集团股份有限公司 | Industrial production method of high-content lutein crystals |
| CN109053517B (en) * | 2018-08-27 | 2020-07-31 | 黄河三角洲京博化工研究院有限公司 | Method for extracting lutein from marigold |
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