CN1259309C - Method for preparing lutein crystal from marigold extractive - Google Patents
Method for preparing lutein crystal from marigold extractive Download PDFInfo
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- CN1259309C CN1259309C CNB2004100460571A CN200410046057A CN1259309C CN 1259309 C CN1259309 C CN 1259309C CN B2004100460571 A CNB2004100460571 A CN B2004100460571A CN 200410046057 A CN200410046057 A CN 200410046057A CN 1259309 C CN1259309 C CN 1259309C
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- deionized water
- lutein
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- lutein crystal
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Abstract
The present invention relates to a method for preparing lutein crystals from marigold extract, which comprises: firstly, under the conditions of stirring and heating, a mixed polar organic solvent liquid and an alkali solution are adopted to saponify the marigold extract, and reaction products are diluted with deionized water, centrifugally separated and dried in vacuum to obtain crude lutein crystals; the crude lutein crystals are recrystallized by tetrahydrofuran/deionized water, and the obtained crystals are washed and dried in vacuum to obtain the product, and the purity of the product can reach more than 95%. The method has the advantages of simple production process, mild reaction conditions, short reaction time and easy realization of industrialization. The product produced by the method of the present invention can be safely and effectively used as a fodder toner and a food colorant, and can also be used as an additive of medicinal health protection products.
Description
Technical field
The present invention relates to natural pigment crystalline process study, use technology of the present invention to prepare highly purified natural pigment from marigold flower medicinal extract.
Background technology
Xenthophylls (lutein) has another name called " plant lutein ", is a kind of carotenoid, extensively is present in the biologies such as flowers, cereal, vegetables, fruit and some algae.Because this natural pigment has lovely luster, strong coloring force, safety non-toxic, advantage such as being rich in nutrition, more and more is subjected to people's favor.Xenthophylls has been widely used in many fields such as food, medicine, makeup and bird feed in recent years.
Studies show that, edible food, medicine and the healthcare products that are rich in xenthophylls can prevent a series of diseases that human body causes because of organ senescence, as the visual deterioration and blind, cardiovascula arteriosclerosis, coronary heart disease and tumor disease etc. that prevent senile eyeball macula retinae degeneration to cause.Add xenthophylls in the animal and fowl fodder, can improve the color and luster and the quality of animal products (as fish, shrimp, chicken and birds, beasts and eggs etc.).Xenthophylls (lutein) and the product that contains xenthophylls reach multi-billion dollar in the sales volume of American market every year, have reached multi-million dollar in the sales volume of world market.Replacing artificial color with natural pigment has been a kind of global trend, and along with the raising of people's level of consumption and the continuous enhancing of health care consciousness, natural pigment will become the main flow in pigment market gradually.Therefore, exploitation xenthophylls product has important social benefit and economic benefit.
The existing both at home and abroad patent of lutein extract and crystalline technology of preparing is delivered, method (CN1120565A) as University Of Qingdao's exploitation from marigold flower extraction lutein resin, this method with the marigold flower plucked through fermentation, dry, pulverize after, by Petroleum ether extraction, concentrate, prepared lutein resins such as deodorization and saponification, product purity is 11-13.5%.The exploitation of Haining phoenix ring chlorophyll company limited prepare the method (CN1436774A) of lutein crystal from marigold flower, this method is at first extracted lutein ester with non-polar solvent from marigold flower under heating condition, under stirring and heating condition, the lutein ester strong solution is carried out saponification then with alkaline solution, with deionized water dilution saponification reaction product, get work in-process again through steps such as separation, washing and vacuum-dryings.Obtain the pure product of xenthophylls with tetrahydrofuran (THF)/deionized water/normal hexane or sherwood oil mixed solvent recrystallization, product purity reaches 95%-98%, but the final extraction yield of product is below 60%, longer 3-10 of saponification reaction time hour.In disclosed xenthophylls production technique, the extraction process of lutein resin is comparative maturity, and large-scale production already, but the preparation of high purity lutein crystal does not also have the formal large-scale production of a family so far.One of them major cause is that production technique is ripe not enough, as product instability, saponification not exclusively, long reaction time, complex process, cost height, solvent be difficult for reclaiming and environment being polluted or the like.
Summary of the invention
The present invention is directed to the problem that exists in the problem, particularly large-scale production that exists among the existing lutein crystal preparation technology and improve, provide a kind of simple, efficient, cost is low, the novel process that is easy to large-scale production.
Operational path of the present invention comprises: the heating lutein extract, add a certain proportion of antioxidant and alkaline solution while stirring xenthophylls is carried out saponification, after treating that saponification reaction is finished, the deionized water that adds certain volume, stir, the centrifugation lutein crystal washs lutein crystal, vacuum-drying respectively with deionized water and lower aliphatic alcoholic solution; Lutein crystal is dissolved in the weakly polar organic solvent, adds deionized water and separate out until lutein crystal, the centrifugation crystal is used deionized water and washing with alcohol crystal respectively, and vacuum-drying is spent the night, and promptly gets the pure product of xenthophylls.The lucifuge of will trying one's best in the reaction process is decomposed to reduce xenthophylls.
Therefore, the invention provides and a kind ofly prepare the method for lutein crystal, it is characterized in that this method comprises following step from marigold flower medicinal extract:
(a). adopt polar organic solvent mixed solution and alkaline solution, under suitable antioxidant existence and heating condition, marigold flower medicinal extract is carried out saponification;
(b). stir adding deionized water down, leave standstill;
(c). the centrifugation lutein crystal;
(d). respectively with deionized water and lower aliphatic alcohols washing c item gained lutein crystal;
(e). the centrifugation lutein crystal;
(f). e item gained lutein crystal is dissolved in the weakly polar organic solvent, adds deionized water until lutein crystal occurring;
(g). repeating step c to e;
(h). vacuum-drying g item gained crystal.
The method according to this invention, the polar organic solvent mixed solution can be the lower aliphatic alcohol mixture described in the step (a), the mixture of preferred alcohol and propylene glycol, most preferably volume ratio is the organic solvent mixed solution of ethanol: propylene glycol=2-3: 7-8.
According to the present invention, alkaline solution can be sodium ethylate, basic metal or alkaline earth metal hydroxides, carbonate described in the step (a), the polar organic solvent of preferred NaOH or KOH, the solution of the ethanol of NaOH or KOH and mixed with propylene glycol solvent for example, wherein the ratio of ethanol and propylene glycol (volume ratio) should be controlled at 20-30%: 70-80%.Described alkaline concentration is preferably: 10-20% (weight percent).The ratio of lutein extract and alkaline solution (volume ratio) should be controlled at 1: 0.8-1.2.
According to the present invention, the saponification reaction temperature is 65-80 ℃ in the step (a), and the reaction times is more than 2 hours, preferred 3-5 hour.According to the present invention, antioxidant described in the step (a) is water-soluble organic oxidation-resistant agent, preferred ethoxyquinoline, and described antioxidant accounts for reaction mixture ratio (weight ratio) and is: 0.2-1%.Use antioxidant to reduce the oxidation ratio of xenthophylls in the saponification reaction process, improve extraction efficiency.
According to the present invention, in the step (b) the deionized water add-on be reaction mixture 15-20 doubly, the control determining alcohol is 5-10%, the preferred 3-5 of time of repose hour.
According to the present invention, in the step (d), with 40-70 ℃ of deionized water, most preferably 50 ℃ of deionized waters are washed till neutrality (pH7.0) with lutein crystal, then, use lower aliphatic alcoholic solution such as methyl alcohol or ethanol more earlier, preferred 75%-95% ethanolic soln washing.
According to the present invention, in the step (f), weakly polar organic solvent is C
2-C
4Epoxide, preferred tetrahydrofuran (THF), usage quantity is controlled at minimum level, promptly just makes the solids CL.When adding the deionized water recrystallization, deionized water adds to lutein crystal separate out till.
According to the present invention, in the step (h), vacuum-drying should be controlled between 25-35 ℃, and time of drying is more than 10 hours, preferred 12-15 hour.
The lutein extract that uses among the present invention is feedstock production by traditional technology with marigold flower, can be the lutein extract that water extraction or alcohol extracting method obtain from marigold flower, and wherein lutein content is 10-12% (weight ratio).
The control of saponification temperature is a key factor in the technology of the present invention, and the too high meeting of temperature causes the xenthophylls degraded, and temperature is crossed low influence saponification speed and saponification degree.
The saponification reaction stage has used antioxidant to reduce the oxidation ratio of xenthophylls in the saponification reaction process among the present invention, and the selection of antioxidant and using method are important factors that influences extraction efficiency.
It is of the present invention that to prepare the method production technique of lutein crystal from marigold extractum simple, the reaction conditions gentleness, and the reaction times is short, easily realizes industrialization.The extraction yield height reaches more than 80%, reaches 95%-98% through high-efficient liquid phase analysis lutein crystal purity.
Embodiment:
Embodiment 1:
Take by weighing 5 gram marigold extractum in 100 milliliters of round-bottomed flasks, add 50 milligrams of ethoxyquinolines, 1.5 milliliters of dehydrated alcohols, 4 milliliters of propylene glycol and 0.8 gram KOH under the induction stirring successively, 75 ℃ of water-baths were reacted 120 minutes down, add 80 ℃ of water-baths of 110 ml distilled waters and stirred the centrifugation lutein crystal at a slow speed 30 minutes; Use deionized water and washing with alcohol crystal respectively, recrystallization after the vacuum-drying.Crystal is dissolved in tetrahydrofuran (THF), adds deionized water until separating out crystallization, the centrifugation lutein crystal is used deionized water and washing with alcohol respectively, and 30 ℃ of vacuum-dryings are spent the night, and get 20 milligrams of crystal 3s.
Embodiment 2:
Take by weighing 600 gram marigold extractum in 5000 milliliters of round-bottomed flasks, add 6 gram ethoxyquinolines, 180 milliliters of dehydrated alcohols, 488 milliliters of propylene glycol and 110 gram KOH under the induction stirring successively, 75 ℃ of water-baths were reacted 120 minutes down, add 80 ℃ of water-baths of 12.8 liters of distilled water and stirred the centrifugation lutein crystal at a slow speed 30 minutes; Use deionized water and washing with alcohol crystal respectively, recrystallization after the vacuum-drying.Crystal is dissolved in tetrahydrofuran (THF), adds deionized water until separating out crystallization, the centrifugation lutein crystal is used deionized water and washing with alcohol respectively, and 30 ℃ of vacuum-dryings are spent the night, and gets crystal 3 9.2 grams.
Claims (9)
1, a kind ofly prepare the method for lutein crystal, it is characterized in that by marigold flower medicinal extract:
(a). adopt ethanol and mixed with propylene glycol liquid and alkaline solution, under ethoxyquinoline existence and heating condition, marigold flower medicinal extract is carried out saponification;
(b). stir adding deionized water down, leave standstill;
(c). the centrifugation lutein crystal;
(d). use deionized water and washing with alcohol c item gained lutein crystal respectively;
(e). the centrifugation lutein crystal;
(f). e item gained lutein crystal is dissolved in C
2-C
4In the solvent of epoxide, add deionized water until lutein crystal occurring;
(g). repeating step c to e;
(h). vacuum-drying g item gained crystal.
2, according to the process of claim 1 wherein in ethanol described in the described step (a) and the mixed with propylene glycol liquid ethanol: the volume ratio=2-3 of propylene glycol: 7-8.
3, according to the process of claim 1 wherein that alkaline solution described in the described step (a) is meant the polar organic solvent of NaOH or KOH, its concentration is: 10-20% (weight percent)
4, according to the process of claim 1 wherein that the saponification reaction temperature is 65-80 ℃ described in the described step (a), the reaction times is more than 2 hours.
5, according to the process of claim 1 wherein that the ratio that the weight of ethoxyquinoline described in the described step (a) accounts for reaction mixture is 0.2-1%.
6, according to the process of claim 1 wherein 15-20 times that the middle deionized water add-on of described step (b) is a reaction mixture, the control determining alcohol is 5-10%.
7, with deionized water lutein crystal is washed till neutrality earlier according to the process of claim 1 wherein that described step (d) is middle, then, again with the washing of 75%-95% ethanolic soln.
8, according to the process of claim 1 wherein the middle C of described step (f)
2-C
4The solvent of epoxide is a tetrahydrofuran (THF), and usage quantity is controlled at solid and just dissolves, when adding the deionized water recrystallization, deionized water adds to lutein crystal separate out till.
9, according to the process of claim 1 wherein that the middle vacuum-drying of described step (h) is controlled between 25-35 ℃, time of drying is more than 10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100460571A CN1259309C (en) | 2004-06-03 | 2004-06-03 | Method for preparing lutein crystal from marigold extractive |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100460571A CN1259309C (en) | 2004-06-03 | 2004-06-03 | Method for preparing lutein crystal from marigold extractive |
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| CN1603308A CN1603308A (en) | 2005-04-06 |
| CN1259309C true CN1259309C (en) | 2006-06-14 |
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| CNB2004100460571A Expired - Fee Related CN1259309C (en) | 2004-06-03 | 2004-06-03 | Method for preparing lutein crystal from marigold extractive |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1793123B (en) * | 2005-12-27 | 2010-10-27 | 成都枫澜科技有限公司 | Process for preparing lutein crystic by drying flower of marigold |
| CN101130512B (en) * | 2007-08-31 | 2010-08-25 | 陕西天润植物化工有限公司 | Method for producing xanthophyll |
| CN101434568B (en) * | 2008-11-19 | 2012-05-30 | 黑龙江省嘉宝生物技术开发有限公司 | 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 |
| 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 |
| CN102174469B (en) * | 2011-01-26 | 2012-11-21 | 宋鑫 | Method for effectively culturing tumor infiltrating lymphocytes (TILs) |
| CN102630822A (en) * | 2012-05-05 | 2012-08-15 | 邯郸市中进天然色素有限公司 | Liquid lutein as feed additive and preparation method thereof |
| CN103058906A (en) * | 2013-01-31 | 2013-04-24 | 甘肃省农垦农业研究院 | Production process of phytoxanthin feed additive |
| CN103319389A (en) * | 2013-06-28 | 2013-09-25 | 大连医诺生物有限公司 | Method for preparing food-grade lutein crystal from marigold extract |
| CN106588733A (en) * | 2016-11-28 | 2017-04-26 | 云南瑞宝生物科技股份有限公司 | Method for preparing xanthophyll from marigold extract |
| 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 |
| CN109503447B (en) * | 2018-12-14 | 2020-12-22 | 山东天音生物科技有限公司 | A method for preparing cryptoxanthin from flos Tagetis Erectae extract |
| CN110663953A (en) * | 2019-10-29 | 2020-01-10 | 内江金瑞莫生物科技有限公司 | Preparation process for polar dispersed lutein and astaxanthin obtained by utilizing lutein |
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