CN1793123B - Process for preparing lutein crystic by drying flower of marigold - Google Patents
Process for preparing lutein crystic by drying flower of marigold Download PDFInfo
- Publication number
- CN1793123B CN1793123B CN 200510022402 CN200510022402A CN1793123B CN 1793123 B CN1793123 B CN 1793123B CN 200510022402 CN200510022402 CN 200510022402 CN 200510022402 A CN200510022402 A CN 200510022402A CN 1793123 B CN1793123 B CN 1793123B
- Authority
- CN
- China
- Prior art keywords
- crystal
- deionized water
- xenthophylls
- lutein
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method to make xanthin crystal from marigold dried flower. It includes the following steps: directly adding KOH.ethanol solution into the marigold dried flower smashed material to take saponifying process; adding water to the raw distilling material, neutralizing by acid material, filtering adding ethyl acetate, removing deposit, distilling raw xanthin; washing by deionized water to form xanthin raw crystal; finally, recrystallizing by tetrahydrofuran and deionized water, washing by deionized water and absolute ethyl alcohol, the xanthin crystal that has purity over 90% would be gained after vacuum drying. It is easy to operate, low cost, high extraction rate, etc.
Description
Technical field
The present invention relates to a kind of method that directly prepares high purity lutein crystal from dried marigold flower.
Background technology
It is a kind of carotenoid that xenthophylls has another name called " plant lutein ", extensively is present in the biologies such as flowers, cereal, vegetables, fruit and some vegetables class.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, the edible food that is rich in xenthophylls, medicine and healthcare products can prevent a series of diseases of asking 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 livestock and poultry product innovation (as fish, shrimp, chicken and birds, beasts and eggs etc.).Xenthophylls reaches multi-billion dollar in the sales volume of American market with the product that contains xenthophylls every year, and sales volume has in the world reached multi-million dollar.Replacing artificial color with natural pigment has been a kind of global trend, 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, and 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, the method from marigold flower extraction lutein resin (the open CN1120565A of Chinese patent) as University Of Qingdao's exploitation, 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 (the open CN1436774A of Chinese patent) 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, again with deionized water dilution saponification reflection product, through separating, steps such as washing and vacuum-drying get work in-process, obtain the pure product of xenthophylls with tetrahydrofuran (THF)/deionized water/normal hexane or sherwood oil mixed solvent recrystallization then, product purity can reach 95%98%, but the final extraction yield of product is below 60%.In disclosed xenthophylls production technique, the extraction process of lutein resin is comparative maturity, and large-scale production already, but the Flower of Aztec Marigold in early stage granulates through fermentation, and second complex process is first destroyed greatlyyer to xenthophylls, have a strong impact on the xenthophylls yield; Noxious solvents such as the sherwood oil of Shi Yonging, normal hexane simultaneously, residual height had both influenced product quality, caused environmental influence again, had also increased cost greatly.
Summary of the invention
The problems referred to above at existing among the existing xenthophylls preparation technology, what the invention provides a kind of work simplification, cost is low, extraction yield is high, pollution is low and is easy to large-scale production directly prepares the processing method of high purity lutein from dried marigold flower.
The technical scheme that the present invention solves the problems of the technologies described above is: it is the marigold flower drying dehydration to pluck directly, the crushed material of pulverizing behind the 10-40 order is a starting material, and be 1 by the feed liquid weight ratio in starting material: 4-6 (the best is 1: 5) adding concentration is the KOH ethanolic soln (this concentration directly adopt be KOH and alcoholic acid weight percent) of 5-11wt% (best be 9-10wt%), directly carrying out saponification handles, in temperature is to stir under the 65-70 ℃ of condition, saponification reaction 2-5 hour, adopt distillating method to remove (promptly reclaiming) ethanol after saponification is finished again, just form the saponification crude extract of mummification; In the saponification crude extract of mummification, add water then and stir, be neutralized to neutrality with acid again, filter and remove solute impurity, separate to such an extent that filter residue is dried processing; And then, adding 6-10 times of (the best is 7 times) weight in the filter residue of oven dry fully stirs in the ethyl acetate of substrate, refilter and remove the throw out impurity that is insoluble to organic solvent, and to isolating filtered liquid employing vacuum distillation method, remove (promptly reclaiming) ethyl acetate, form the xenthophylls crude product, from then on finish the leaching process of xenthophylls crude product; Secondly with the xenthophylls crude product deionized water wash that extracts, remove the organic impurities that is dissolved in deionized water once more, separate out the lutein crystal thing simultaneously, the filtering separation after drying is handled filter residue and is promptly got the xenthophylls coarse crystallization; At last, the xenthophylls coarse crystallization that obtains is carried out recrystallization to be handled, be about to the xenthophylls coarse crystallization and be dissolved in tetrahydrofuran (THF), cross filter to remove insoluble impurity after, use the deionized water recrystallization, use deionized water and absolute ethanol washing again after isolating crystalline substance,, be drying to obtain purity at the lutein crystal finished product more than 90% through separation to remove impurity such as residual organic solvent, water and organic and inorganic thing.
In the aforesaid method, the KOH in the KOH ethanolic soln can be replaced by NaOH; The removal alcoholic acid distillating method that saponification reaction liquid is adopted both was heated to 78 ℃ of distillatory methods under the normal pressure, also vacuum decompression distillatory method; In the saponification crude extract being added the water stirring, the adding weight of its water has been 4-8 times (the best is 5 times) of expecting, and water temp is 0-80 ℃; The acid that uses in the neutralization reaction is meant one or more the mixture in the organic acid compounds such as inorganic acid compounds such as phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid and formic acid, acetate, citric acid, and its consumption is so that the pH value of neutralizer reaches 7 is as the criterion.
In preceding method, it is to dry to handle 5-24 hour under ℃ condition of temperature≤60 that neutralization reaction back separation is obtained filter residue; The adding weight that is used to wash the deionized water of xenthophylls crude product is that each 5-10 is doubly to substrate, the temperature of deionized water is 0-60 ℃, washs 3-5 time, filters to isolate filter residue then, and under room temperature or 25 ℃ to its vacuum-drying 24-48 hour, promptly get the xenthophylls coarse crystallization; In the recrystallization of xenthophylls coarse crystallization is handled, the consumption that is used for the tetrahydrofuran solvent of dissolve lutein coarse crystallization thing is that 9-15 times of (the best is 10 times) weight is in substrate, the stirring and dissolving after-filtration removes filter residue, in filtered liquid, add deionized water, until separating out lutein crystal, adopt centrifugal separation method to isolate crystal then, and to it respectively with deionized water and the absolute ethanol washing of 2-4 times of weight in substrate, filter out crystallisate then, under room temperature or 25 ℃ of conditions dry 24-48 hour again, promptly obtain finished product of the present invention.
The present invention has following advantage: 1. work simplification, directly, can obtain highly purified lutein crystal through steps such as saponification, neutralization, precipitation, extraction, crystallization, recrystallizations, and reduced Flower of Aztec Marigold fermentation granulation and two complicated procedures of forming of preparation lutein ester; 2. xenthophylls destruction is all little with loss among the preparation technology, so the xenthophylls extraction yield can reach 70%; 3. preparation cost can reduce 20-40%, and organic solvent toxicity is low and be easy to recovery, and is residual few, also little to the pollution of environment; 4. be applicable to industrial scale production, and the xenthophylls that finally obtains meets the European Pharmacopoeia requirement.
Specific implementation method
Embodiment 1
1), extract dried marigold flower (fermentation) 1kg, be crushed to about 20 order powder (cross 10-40 order all can); Is 1: 5 adding KOH ethanolic soln (KOH: ethanol=467g: 5L), be to stir saponification reaction 3 hours under the 65-70 ℃ of condition in temperature to it by the feed liquid weight ratio; Remove ethanol, the saponification crude extract that must do in 55 ℃ of vacuum decompression distillations (or under normal pressure, being heated to 78 ℃ of distillations) then.
2), in the saponification crude extract, add 5 liters in water, water temp is 20 ℃, stir about 30 minutes fully is neutralized to neutrality (PH=7) with phosphoric acid.Filter filter residue 50 ℃ down oven dry handled 16 hours; Then, in the filter residue of oven dry, add 7 times, stirred 30 minutes, filter and remove throw out, remove ethyl acetate with vacuum distillation method again, get the xenthophylls crude product to the ethyl acetate of filter residue weight.
3), in above-mentioned xenthophylls crude product each deionized water that adds 5 times of weight, the temperature of deionized water is 25 ℃ (temperature of deionized water can be selected between 0-60 ℃), washs 3 times; Filter to isolate the crystal thing then, and vacuum-drying at room temperature 32 hours, xenthophylls coarse crystal 31.69 grams, lutein content is 65.3%.
4), the xenthophylls coarse crystal is dissolved in the tetrahydrofuran (THF) of 10 times of weight, stirs and dissolve after-filtration fully and remove slag, add the deionized water of capacity at filtered liquid, until separating out lutein crystal; Then, the centrifugation lutein crystal, use the deionized water of 2 times of weight and absolute ethanol washing, precipitation more respectively, filter out crystallisate, got lutein crystal 19.6 grams in 35 hours eventually in room temperature vacuum-drying again, lutein content reaches 95.75% (with the visible fully photometry of UV/), and trans-lutein, zeaxanthin and other carotenoid analyzed wherein with PHLC are respectively 92.17%, 6.20%, 1.63%.
Embodiment 2
1), extract dried marigold flower (fermentation) 2kg, be crushed to about 20 order powder (cross 10-40 order all can); Is 1: 6 adding KOH ethanolic soln (KOH: ethanol=1300g: 12L), be to stir saponification reaction 4 hours under the 65-70 ℃ of condition in temperature to it by the feed liquid weight ratio; Remove ethanol, the saponification crude extract that must do in 55 ℃ of vacuum decompression distillations (or under normal pressure, being heated to 78 ℃ of distillations) then.
2), in the saponification crude extract, add 12 liters in water, water temp is 22 ℃, stir about 30 minutes fully is neutralized to neutrality (PH=7) with hydrochloric acid.Filter filter residue 60 ℃ down oven dry handled 12 hours; Then, in the filter residue of oven dry, add the ethyl acetate of 7-9 times of weight, stirred 30 minutes, filter and remove throw out, remove ethyl acetate with vacuum distillation method again, get the xenthophylls crude product.
3), in above-mentioned xenthophylls crude product each deionized water that adds 10 times of weight, the temperature of deionized water is 22 ℃, washs 4 times; Filter to isolate the crystal thing then, and vacuum-drying 40 hours under the room temperature, xenthophylls coarse crystal 63.55 grams, lutein content is 66.7%.
4), the xenthophylls coarse crystal is dissolved in the tetrahydrofuran (THF) of 13 times of weight, stirs and dissolve after-filtration fully and remove slag, add the deionized water of capacity at filtered liquid, until separating out lutein crystal; Then, the centrifugation lutein crystal, use the deionized water of 4 times of weight and 3 times of weight absolute ethanol washings, precipitation more respectively, filter out crystallisate, got lutein crystal 41.3 grams in 35-40 hour eventually in room temperature vacuum-drying again, lutein content reaches 95.45% (with the visible fully photometry of UV/), and trans-lutein, zeaxanthin and other carotenoid analyzed wherein with PHLC are respectively 92.17%, 6.20%, 1.63%.
What deserves to be mentioned is that among above-mentioned two embodiment: the KOH in the KOH ethanolic soln can be replaced by NaOH; The add-on of the water that relates among the preparation technology, deionized water, ethyl acetate, tetrahydrofuran (THF), dehydrated alcohol all can add by the scope of summary of the invention indication, and the time of saponification processing and drying treatment too.
Claims (9)
1. method for preparing lutein crystal by dried marigold flower, its marigold flower convection drying dehydration to pluck, and to pulverize 10-40 purpose crushed material be starting material, it is characterized in that it is 1 by the feed liquid weight ratio in starting material: it is the KOH ethanolic soln of 5-11wt% that 4-6 adds concentration, being 65-70 ℃ in temperature stirs down, saponification reaction 2-5 hour, adopt distillating method to remove ethanol again, form the saponification crude extract of mummification; In the saponification crude extract, add water then and stir, be neutralized to neutral after-filtration with acid and separate, and oven dry is handled to filter residue; The ethyl acetate that adds 6-10 times of weight in the filter residue of oven dry stirs, and filters and removes throw out, adopts vacuum distillation method to remove ethyl acetate to filtrate again, forms the xenthophylls crude product; Secondly, with the xenthophylls crude product deionized water wash that extracts, get the xenthophylls coarse crystallization after the separation drying; At last, the xenthophylls coarse crystallization is dissolved in tetrahydrofuran (THF), and uses the deionized water recrystallization, isolate the crystal thing after, use deionized water and absolute ethanol washing again, be drying to obtain purity at the lutein crystal finished product more than 90% through separation.
2. according to claim 1ly prepare the method for lutein crystal by dried marigold flower, it is characterized in that described starting material and KOH ethanolic soln blended feed liquid weight ratio are 1: 5, the weight percent of KOH is 9%-10% in the KOH ethanolic soln.
3. according to claim 1ly prepare the method for lutein crystal, it is characterized in that the removal alcoholic acid distillating method that saponification reaction liquid adopts is meant under normal pressure, being heated to 78 ℃ of distillations or vacuum decompression distillatory method by dried marigold flower.
4. according to claim 1ly prepare the method for lutein crystal, it is characterized in that the saponification crude extract is added during water stirs by dried marigold flower, the adding weight of its water be starting material 4-8 doubly, water temperature is 0-80 ℃.
5. the method for preparing lutein crystal by dried marigold flower according to claim 1, the acid that it is characterized in that being used for neutralization reaction is meant one or more mixture of phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid inorganic acid compound and formic acid, acetate, citric acid organic acid compound, and its consumption is so that the pH value of neutralizer is 7 to be as the criterion.
6. according to claim 1ly prepare the method for lutein crystal, it is characterized in that the separating obtained filter residue of neutralization reaction after-filtration dried under temperature≤60 ℃ and handled 5-24 hour by dried marigold flower.
7. the method for preparing lutein crystal by dried marigold flower according to claim 1, the adding weight that it is characterized in that being used to washing the deionized water of xenthophylls crude product is that each 5-10 is doubly to substrate, the temperature of deionized water is 0-60 ℃, wash 3-5 time, filter to isolate filter residue then, and at room temperature or under 25 ℃ to its vacuum-drying 24-48 hour, promptly get the xenthophylls coarse crystallization.
8. the method for preparing lutein crystal by dried marigold flower according to claim 1, the tetrahydrofuran (THF) consumption that it is characterized in that being used for the dissolve lutein coarse crystal is that 9-15 times of weight is in substrate, the stirring and dissolving after-filtration removes filter residue, in filtered liquid, add deionized water, until separating out lutein crystal.
9. the method for preparing lutein crystal by dried marigold flower according to claim 1, it is characterized in that adopting centrifugation to go out crystal behind the recrystallization, and to it respectively with deionized water and the absolute ethanol washing of 2-4 times of weight in substrate, filter out crystallisate then, again in room temperature or 25 ℃ of following vacuum-dryings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510022402 CN1793123B (en) | 2005-12-27 | 2005-12-27 | Process for preparing lutein crystic by drying flower of marigold |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510022402 CN1793123B (en) | 2005-12-27 | 2005-12-27 | Process for preparing lutein crystic by drying flower of marigold |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1793123A CN1793123A (en) | 2006-06-28 |
| CN1793123B true CN1793123B (en) | 2010-10-27 |
Family
ID=36804785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510022402 Expired - Fee Related CN1793123B (en) | 2005-12-27 | 2005-12-27 | Process for preparing lutein crystic by drying flower of marigold |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1793123B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102174005A (en) * | 2011-01-25 | 2011-09-07 | 石河子大学医学院第一附属医院 | Method for extracting lutein from marigold dried flowers |
| WO2013097056A1 (en) * | 2011-12-31 | 2013-07-04 | 晨光生物科技集团股份有限公司 | Method for preparing lutein crystal |
| CN103664724B (en) * | 2012-09-12 | 2015-07-08 | 中国科学院大连化学物理研究所 | Method for extracting zeaxanthine from physalis alkekengi and fruits through one-pot method |
| 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 |
| CN103304463A (en) * | 2013-06-18 | 2013-09-18 | 哈尔滨宝德生物技术开发有限公司 | Method for preparing lutein from marigold particles |
| 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 |
| CN103992255B (en) * | 2014-05-17 | 2017-01-18 | 云南云药医药研究有限公司 | Method for preparing high-purity xanthophylls with calendula officinalis |
| CN105669510A (en) * | 2016-02-29 | 2016-06-15 | 苏州市贝克生物科技有限公司 | Method for extracting lutein in marigold |
| CN106748947B (en) * | 2017-02-20 | 2018-06-26 | 青岛藻蓝生物有限公司 | It is a kind of to combine the method for preparing lutein ester and lutein |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1310584A (en) * | 1997-05-14 | 2001-08-29 | 凯敏工业公司 | Method for the conversion of xanthophylls in plant material |
| WO2004018417A1 (en) * | 2002-08-26 | 2004-03-04 | Kancor Flavours And Extracts Ltd | An improved process for the preparation of xanthophyll crystals |
| CN1603308A (en) * | 2004-06-03 | 2005-04-06 | 成都枫澜科技有限公司 | Method for preparing lutein crystal from marigold extractive |
-
2005
- 2005-12-27 CN CN 200510022402 patent/CN1793123B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1310584A (en) * | 1997-05-14 | 2001-08-29 | 凯敏工业公司 | Method for the conversion of xanthophylls in plant material |
| WO2004018417A1 (en) * | 2002-08-26 | 2004-03-04 | Kancor Flavours And Extracts Ltd | An improved process for the preparation of xanthophyll crystals |
| CN1603308A (en) * | 2004-06-03 | 2005-04-06 | 成都枫澜科技有限公司 | Method for preparing lutein crystal from marigold extractive |
Non-Patent Citations (3)
| Title |
|---|
| US 5382714 A, |
| 张德军.叶黄素的提取及制备进展.化学工程师 7期.2005,(7),37-39. |
| 张德军.叶黄素的提取及制备进展.化学工程师 7期.2005,(7),37-39. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1793123A (en) | 2006-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1793123B (en) | Process for preparing lutein crystic by drying flower of marigold | |
| US6329557B1 (en) | Purification of xanthophylls from marigold extracts that contain high levels of chlorophylls | |
| DE60317770T3 (en) | astaxanthin | |
| US7622599B2 (en) | Isolation and purification of carotenoids from marigold flowers | |
| KR100838435B1 (en) | Extract from the pods of lupin seeds containing lupeol | |
| CN1259309C (en) | Method for preparing lutein crystal from marigold extractive | |
| CA2696259C (en) | A process for isolation of carotenoids from plant sources | |
| CN103319389A (en) | Method for preparing food-grade lutein crystal from marigold extract | |
| CN101130512A (en) | Method for producing xanthophyll | |
| CN102633877A (en) | Preparation method of collagen powder by using fish skin and fish scale | |
| US8481769B2 (en) | Isolation and purification of cartenoids from marigold flowers | |
| CN101429146B (en) | High purity xanthophyll crystal produced with marigold petal and producing method thereof | |
| CN105189526A (en) | Method for preparing coumestrol or coumestrin | |
| CN112500448B (en) | Method for extracting laxogenin from Liliaceae Allium plant | |
| US7297803B2 (en) | Process for the preparation of lutein ester concentrate | |
| US7390914B2 (en) | Process for the preparation of lutein ester concentrate | |
| KR20050097698A (en) | A method for producing oleanolic acid and ursolic acid from persimmon peel | |
| BG65598B1 (en) | Method for silimarin isolation from the fruits of silybum marianum (l) gaerth | |
| DE10313077A1 (en) | Production of a bioflavonoid preparation useful as or in a dietary supplement, food or animal feed comprises extracting plant material with aqueous alcohol and concentrating the extract | |
| RU2493172C1 (en) | Method for silver fir wood green | |
| CN117820185A (en) | Extraction method and application of astaxanthin | |
| CN106565850A (en) | Extraction method for polysaccharides in cockles | |
| JP2009001535A (en) | Method for preparing composition having high lutein content and lutein |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| CI01 | Correction of invention patent gazette |
Correction item: deemed to have been withdrawn Correct: delete False: Wrong announcement Number: 16 Page: 1668 Volume: 25 |
|
| ERR | Gazette correction |
Free format text: CORRECT: DEEMED WITHDRAWAL; FROM: WRONG PUBLICATION TO: DELETE |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101027 Termination date: 20151227 |