CN1405235A - Method for preparing high-purity lycopene - Google Patents
Method for preparing high-purity lycopene Download PDFInfo
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- CN1405235A CN1405235A CN 02146560 CN02146560A CN1405235A CN 1405235 A CN1405235 A CN 1405235A CN 02146560 CN02146560 CN 02146560 CN 02146560 A CN02146560 A CN 02146560A CN 1405235 A CN1405235 A CN 1405235A
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- 235000012661 lycopene Nutrition 0.000 title claims description 29
- 239000001751 lycopene Substances 0.000 title claims description 29
- JEVVKJMRZMXFBT-XWDZUXABSA-N Lycophyll Natural products OC/C(=C/CC/C(=C\C=C\C(=C/C=C/C(=C\C=C\C=C(/C=C/C=C(\C=C\C=C(/CC/C=C(/CO)\C)\C)/C)\C)/C)\C)/C)/C JEVVKJMRZMXFBT-XWDZUXABSA-N 0.000 title claims description 26
- OAIJSZIZWZSQBC-GYZMGTAESA-N lycopene Chemical compound CC(C)=CCC\C(C)=C\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C=C(/C)CCC=C(C)C OAIJSZIZWZSQBC-GYZMGTAESA-N 0.000 title claims description 26
- 229960004999 lycopene Drugs 0.000 title claims description 26
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- 235000007688 Lycopersicon esculentum Nutrition 0.000 claims abstract description 25
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Abstract
The invention refers to a manufacturing method of a kind of high purity tomato red elements, its characters lie in: redeye is extracted after it is dehydrated by carbinol or ethanol, the extracted liquid is frozen, crystaled and dried to get the 90-93% purity tomato red element, the above products are separated, purified, concentrated and frozen by reverse phase chromatogram, and gets the tomato red elements with purity above 99%.
Description
Technical field
The present invention relates to a kind of preparation method of high purity Lyeopene, belong to food-processing and medical technical field.
Background of invention
Lyeopene is a kind of of carotenoid, the discovered in recent years Lyeopene has than other carotenoid more superior biological activity is arranged, its oxidation-resistance, the performance of removing free radical is the strongest in carotenoid, the ability of cancellation singlet oxygen is 100 times of the present antioxidant vitamin E that uses always, 3 times of beta carotene, the Lyeopene that studies show that in recent years is diseases prevention, the critical function factor of curing the disease, it has the generation of preventing cancer, suppress the formation of LDL cholesterol oxide, prevention coronary heart disease, promote intercellular normal combination, can promote to have and keep synthesizing of the normal conjugated protein of iuntercellular, activating immune cell, the effect of anticancer multiplicaiton factor prevents and treats the function of some prostatosis.
Because the peculiar function of Lyeopene, the healthcare products listing of Lyeopene was just arranged from 1994, the output value is in continuous growth, clinical experiment has also obtained breakthrough, the prospect of making healthcare products with Lyeopene is considerable, someone predicts that it may develop into three similar drugs, therefore, produces Lyeopene on a large scale and preparation high purity Lyeopene is necessary.
The preparation lycopene method is a lot of at present, majority extracts from tomato and tomato product, as disclose in the CN1298904A document a kind of from tomato-sauce production purity in 10% lycopene method, employing adds water stirring, centrifuge dehydration, multisteps such as alkali cleaning, washing, drying and crushing, heating extraction, flash distillation, crystallization obtain lycopene crystal suddenly, its weak point is that product purity is not high, operates very complicatedly, produces wayward; Disclose a kind of employing tomato-sauce drying in the CN1296038A document, pulverize back dress post, use ethanol, acetone drip washing, still do not break away from complicated drying, crushing operation, and solvent consumption is huge, be unfavorable for industrial production, product purity is between 40-86.7%, quality is wayward, a kind of preparation method of Lyeopene is disclosed in the CN1176577A document, in whizzer separate slurries with separating after remaining slag through extruding with tomato, with 50 ℃ of ethyl acetate extractions, it is 5% oleo-resinous that evaporation concentration can obtain containing Lyeopene, disclose the contrary chromatography of employing high speed flow in the CN1316468A document and from the Lyeopene crude product, separated the highly purified Lyeopene method of preparation, this method need be used multiple organic solvent, comprising hypertoxic acetonitrile is arranged, chloroform, tetracol phenixin, methyl alcohol etc., and the separation scale only limits to the milligram level, its product purity can reach more than 95%, does not sell but have yet so far greater than the product of 95% purity.
Summary of the invention
Purpose of the present invention is the shortcoming and deficiency in order to overcome above-mentioned prior art just, and provide the preparation method of the high purity Lyeopene that a kind of method is simple, the rate of recovery is high, thereby for food, health care, medical aspect provide the Lyeopene of corresponding purity, in particular for the medicinal lycopene product that provides more than 99%.
The objective of the invention is to realize by following technical proposal:
The preparation method of high purity Lyeopene is characterized in that it is undertaken by following step:
A) ethanol or the methyl alcohol with 95% purity of tomato-sauce and 1-10 times of weight adds stainless steel reactor
In, stir after-filtration dehydration in 0.5-3 hour at normal temperature condition, obtain the tomato residue of soya;
B) the tomato residue of soya is added the low carbon fatty acid ester and/or the low-carbon (LC) halohydrocarbon of 2.5-1.5 times of weight, at nitrogen
Protection is heated to 30-70 ℃ down, stirs and extracts extraction times three times in 0.5-2 hour
More than, filtering and obtain extraction liquid, tomato pomace is stand-by;
C) again with extraction liquid freezing and crystallizing under 0--20 ℃ of temperature, back ageing 4 hours, the usefulness separated out to be crystallized
A little 95% purity washing with alcohol crystallization, drying obtains the lycopene product of 90-93% purity,
Mother liquor concentrates the oleo-resinous product that obtains containing Lyeopene 5-8%;
D) with c) the lycopene product of 90-93% purity load on high molecular polymer according to a conventional method
On the filler stationary phase, there is the filler of Lyeopene to place reverse-phase chromatographic column to divide this load again
From, at first with methyl alcohol or ethanol elution, use compound eluent wash-out then, routinely gradient elution
Method cis wash-out is collected target fraction, and under nitrogen protection, the vacuum concentration freezing and crystallizing is done
Dry, obtain the lycopene product of 99% above purity.
The also available new fresh tomato of described tomato-sauce separates clear liquid through pulverizing, behind centrifugal, segregation, decortication and the seed, dripping the aqueous solution of 10% sodium hydroxide under slowly stirring, and filters and obtains tomato-sauce; Described low carbon fatty acid ester is n-butyl acetate, isopropyl acetate, ethyl acetate, methyl acetate; The low-carbon (LC) halohydrocarbon is methylene dichloride, ethylene dichloride and chloroform, and low carbon fatty acid ester and low-carbon (LC) halohydrocarbon can be one or both combinations wherein; Described high molecular polymer filler stationary phase is a multi-hole type polystyrene divinylbenzene multipolymer, multi-hole type crosslinked polypropylene enoate copolymer, or multi-hole type crosslinked methacrylic acid copolymer, and diameter is at 50-10 μ m, specific surface area 100-800m
2/ g is than cell size 50-80Vol%; Described compound eluent is by containing in methyl alcohol, ethanol, Virahol or the butanols of A component or the above-mentioned alcohol＜10% the aqueous solution, wherein a kind of mutually compound of methylene dichloride, ethylene dichloride or the chloroform of a kind of and B component wherein, ethyl acetate, butylacetate, the A group is 10 with B group compositely proportional: 90-90: 10; Described chromatographic column is the chromatographic bed of PRP-6 type high molecular polymer filler; Described compound eluent adopts gradient elution, and being increases B group component concentration gradually, and substep is collected and obtained target component; The Lyeopene goods of described 99% above purity are all-trans lycopene.
Tomato-sauce of the present invention is to be provided by basic tomato product company limited in the Xinjiang.
It is the sterile packed product that is processed by ripe, complete, scarlet tomato, does not contain any additives.
The Oranoleptic indicator:
The sauce body is consistent bright red, and free from extraneous odour is evenly fine and smooth, thickness appropriateness, inclusion-free.
Physical and chemical index:
Total solid 15-18%
Tomato solid content 〉=65%
Lyeopene 〉=50mg/100g
Viscosity (cm/30s; 12.5brix/20 ℃) heat broken＜4.5 cold breaking＜7-9
PH＝4.2±0.2
Sn≤100mg/kg
Cu≤10mg/kg
Pb≤1mg/kg
As≤0.5mg/kg
Microbiological indicator;
Mold count≤40% visual field
Pathogenic bacterium must not detect.
The product of method preparation of the present invention is through UV-Vis spectroscopic analysis, HPLC analysis, Infrared spectroscopy, mass spectroscopy, spectral analysis of the nuclear magnetic resonance, proved that the product that obtains is the pure product of trans Lyeopene, contrasted its content greater than 99% with external authoritative document mol extinction value.
Owing to take technique scheme, make the technology of the present invention compared with the prior art have following advantage and effect:
A) preparation method is simple, realizes that easily suitability for industrialized production and cost are low, yield is high, purity is high;
B) raw material of Cai Yonging does not have any toxicity, guarantees the quality and the edible security of product;
C) the no three wastes, free from environmental pollution.
Description of drawingsFig. 1 is the HPLC analytical results of embodiment 2 products; Fig. 2 is the UV-Vis spectroscopic analysis result of embodiment 2 products; Fig. 3 is the results of IR of embodiment 2 products; Fig. 4 is the mass spectrometry results of embodiment 2 products; Fig. 5 is the spectral analysis of the nuclear magnetic resonance result of embodiment 2 products.
Embodiment
The used tomato-sauce of present embodiment is provided by basic tomato product company limited in the Xinjiang.The content of Lyeopene is 100mg/100g.
Embodiment 1
Get tomato-sauce 5kg and add 95% purity ethanol 5kg stirring at normal temperature after-filtration dehydration in 3 hours in stainless steel reactor; obtain tomato residue of soya 1.2kg, again this tomato-sauce is added n-butyl acetate 2.5kg in reaction flask, under nitrogen protection; heat 70 ℃; stir filtration in 2 hours, obtain extraction liquid, again filter residue is added the 2kg n-butyl acetate; carry out reextraction by above-mentioned condition; filtration obtains extraction fluid, filter residue is added the 2kg n-butyl acetate again, advances three extractions, filters by above-mentioned condition.Three extraction liquids are incorporated in-10--12 ℃ following freezing and crystallizing, ageing is 4 hours after to be crystallized the separating out, with a little 95% purity washing with alcohol crystallization, drying obtains the lycopene product of 92% purity, the mother liquor concentrate drying obtains containing the oleo-resinous product of Lyeopene 8.2%, and the lycopene product of 92% purity that obtains is loaded on the multi-hole type polystyrene divinylbenzene multipolymer stationary phase according to a conventional method, its particle diameter 50-100 μ m is than the long-pending 100m of table
2/ g; than cell size 50Vol%; this load is had the filler of Lyeopene to place φ 26 high 600mm chromatographic column front ends to separate, methanol-eluted fractions is at first used 90: 10 methyl alcohol and methylene dichloride wash-out then again; 80: 20 methyl alcohol and methylene dichloride wash-out; 60: 40 methyl alcohol and methylene dichloride wash-out are collected elutriant respectively, under nitrogen protection; the vacuum concentration lyophilize obtains 99.5% high purity lycopene product.
Embodiment 2
Get tomato-sauce 5kg and add 95% purity ethanol 25kg stirring at normal temperature after-filtration dehydration in 1.5 hours in stainless steel reactor, obtain tomato residue of soya 1.15kg, again this tomato-sauce is added butylacetate 2.3kg in reaction flask, under nitrogen protection, heat 55 ℃, stir filtration in 1.5 hours, obtain extraction liquid; Again filter residue is added the 1.85kg butylacetate, carry out reextraction, filter and obtain extraction fluid, again filter residue is added the 2.0kg butylacetate, advance three extractions, filter by above-mentioned condition by above-mentioned condition.Three extraction liquids are incorporated in 0--5 ℃ of following freezing and crystallizing, ageing is 4 hours after to be crystallized the separating out, with a little 95% purity washing with alcohol crystallization, drying obtains the lycopene product of 91% purity, the mother liquor concentrate drying obtains containing the oleo-resinous product of Lyeopene 8.5%, and the lycopene product of 92% purity that obtains is loaded on the multi-hole type crosslinked methacrylic acid copolymer stationary phase according to a conventional method, its particle diameter 80-100 μ m is than the long-pending 500m of table
2/ g; than cell size 60Vol%; again this load there is the filler of Lyeopene to place the high 600mm chromatographic column of φ 26mm front end to separate; at first use ethanol elution, use 90: 10 ethanol and chloroform wash-out then, 60: 40 ethanol and chloroform wash-out; 10: 90 ethanol and chloroform wash-out are collected elutriant respectively; under nitrogen protection, the vacuum concentration lyophilize obtains 99.2% high purity lycopene product.
Embodiment 3
Get tomato-sauce 5kg and add 95% purity ethanol 50kg stirring at normal temperature after-filtration dehydration in 0.5 hour in stainless steel reactor, obtain tomato residue of soya 1.1kg, again this tomato-sauce is added butylacetate 2.8kg in reaction flask, under nitrogen protection, heat 30 ℃, stir filtration in 1 hour, obtain extraction liquid; Again filter residue is added the 1.8kg butylacetate, carry out reextraction, filter and obtain extraction fluid, again filter residue is added the 1.6kg butylacetate, advance three extractions, filter by above-mentioned condition by above-mentioned condition.Three extraction liquids are incorporated in-15--20 ℃ following freezing and crystallizing, ageing is 4 hours after to be crystallized the separating out, with a little 95% purity washing with alcohol crystallization, drying obtains the lycopene product of 93% purity, the mother liquor concentrate drying obtains containing the oleo-resinous product of Lyeopene 7.9%, and the lycopene product of 92% purity that obtains is loaded on the multi-hole type crosslinked polypropylene enoate copolymer stationary phase according to a conventional method, its particle diameter 50-80 μ m is than the long-pending 80m of table
2/ g than cell size 80Vol%, has this load the filler of Lyeopene to place the high 600mm chromatographic column of φ 26mm front end to separate again.Earlier use methanol-eluted fractions, use 70: 30 methyl alcohol and chloroform wash-out then, 50: 50 methyl alcohol and chloroform wash-out, 30: 70 methyl alcohol and chloroform wash-out are collected elutriant respectively, and under nitrogen protection, the vacuum concentration lyophilize obtains 99.8% high purity lycopene product.
Embodiment 4
With new fresh tomato pulverize according to a conventional method, centrifugal, peel, take off seed, the preparation tomato-sauce, get 5kg tomato-sauce and stir slowly adding 10% aqueous sodium hydroxide solution, separate scarfing cinder, filtration obtains tomato residue of soya 1.0kg, the method of pressing embodiment 1 extracts three times, extraction liquid with ordinary method dehydration after freezing, crystallization, washing, obtain the lycopene product of 90% purity and contain Lyeopene 5.2% oleo-resinous product, the lycopene product of above-mentioned 90% purity is obtained 99.7% lycopene product by the method for embodiment 1 through chromatogram purification.Embodiment 5
Get 5kg tomato-sauce and stir slowly adding 10% aqueous sodium hydroxide solution, separate scarfing cinder, filtration obtains tomato residue of soya 1.1kg, the method of pressing embodiment 1 extracts three times, extraction liquid with ordinary method dehydration after freezing, crystallization, washing, obtain the lycopene product of 90% purity and contain Lyeopene 5.2% oleo-resinous product, the lycopene product of above-mentioned 90% purity is obtained 99.6% lycopene product by the method for embodiment 1 through chromatogram purification.
The analytical results of embodiment 2 by Fig. 1, Fig. 2, Fig. 3, Fig. 4, Fig. 5, shown in.Fig. 1 is that HPLC analyzes, with Tianjin, island LC-10A HPLC, the C18 chromatographic column, 99.2% Fig. 2 Uv-Vis spectroscopic analysis, maximum absorption band 502,470, the literary composition of 444nm and all-trans lycopene
The value of offering is consistent, and the molar extinction coefficient at the 470nm place is 185100, with literature value 184900 mutually
Symbol proves that its purity has reached documentation standards product level.Fig. 3 is the IR spectrogram, and is in full accord with document, and polyene structure is at 1629cm in the Lyeopene molecule
-1, 1552
Cm
-1Show weak absorption band, at 959cm
-1Show that strong absorption band proof product of the present invention reaches foreign literature
Standard substance purity.Fig. 4 is a MALDI-TOF mass spectrum numerical value, and the molecular-weight average of measuring 536.6 is consistent with theoretical value 536.86.Fig. 5 is proton spectra, shows in the products molecule among the figure only to have saturated c h bond and conjugated alkene key, with tomato
Red pigment structure unanimity does not have the spectral information of other group.
Claims (8)
1. the preparation method of high purity Lyeopene is characterized in that it is undertaken by following step:
A) ethanol or the methyl alcohol with 95% purity of tomato-sauce and 1-10 times of weight adds stainless steel reactor
In, stir after-filtration dehydration in 0.5-3 hour at normal temperature condition, obtain the tomato residue of soya;
B) the tomato residue of soya is added the low carbon fatty acid ester and/or the low-carbon (LC) halohydrocarbon of 2.5-1.5 times of weight, at nitrogen
Protection is heated to 30-70 ℃ down, stirs and extracts extraction times three times in 0.5-2 hour
More than, filtering and obtain extraction liquid, tomato pomace is stand-by;
C) again with extraction liquid freezing and crystallizing under 0--20 ℃ of temperature, back ageing 4 hours, the usefulness separated out to be crystallized
A little 95% purity washing with alcohol crystallization, drying obtains the lycopene product of 90-93% purity,
Mother liquor concentrates the oleo-resinous product that obtains containing Lyeopene 5-8%;
D) with c) the lycopene product of 90-93% purity load on high molecular polymer according to a conventional method
On the filler stationary phase, there is the filler of Lyeopene to place reverse-phase chromatographic column to divide this load again
From, at first with methyl alcohol or ethanol elution, use compound eluent wash-out then, routinely gradient elution
Method cis wash-out is collected target fraction, and under nitrogen protection, the vacuum concentration freezing and crystallizing is done
Dry, obtain the lycopene product of 99% above purity.
2. preparation method according to claim 1, it is characterized in that the also available new fresh tomato of described tomato-sauce through pulverize, behind centrifugal, segregation, decortication and the seed, under slowly stirring, drip the aqueous solution of 10% sodium hydroxide, separate clear liquid, filter and obtain tomato-sauce.
3. preparation method according to claim 1 is characterized in that described low carbon fatty acid ester is n-butyl acetate, isopropyl acetate, ethyl acetate, methyl acetate; The low-carbon (LC) halohydrocarbon is methylene dichloride, ethylene dichloride and chloroform, and low carbon fatty acid ester and low-carbon (LC) halohydrocarbon can be one or both combinations wherein.
4. preparation method according to claim 1, it is characterized in that described high molecular polymer filler stationary phase is a multi-hole type polystyrene divinylbenzene multipolymer, multi-hole type crosslinked polypropylene enoate copolymer, or multi-hole type crosslinked methacrylic acid copolymer, diameter is at 50-10 μ m, specific surface area 100-800m
2/ g is than cell size 50-80Vol%.
5. preparation method according to claim 1, it is characterized in that described compound eluent is by containing in methyl alcohol, ethanol, Virahol or the butanols of A component or the above-mentioned alcohol＜10% the aqueous solution, wherein a kind of mutually compound of methylene dichloride, ethylene dichloride or the chloroform of a kind of and B component wherein, ethyl acetate, butylacetate, the A group is 90 with B group compositely proportional: 10-10: 90.
6. preparation method according to claim 1 is characterized in that described chromatographic column is the chromatographic bed of PRP-6 type high molecular polymer filler.
7. preparation method according to claim 5 is characterized in that described compound eluent adopts gradient elution, is to increase B group component concentration gradually, and substep is collected and obtained target component.
8. preparation method according to claim 1, the Lyeopene goods that it is characterized in that described 99% above purity are all-trans lycopene.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315953C (en) * | 2003-09-15 | 2007-05-16 | 广州优宝工业有限公司 | Preparation method of lycopene |
| CN1965693B (en) * | 2006-06-13 | 2012-12-05 | 新疆屯河投资股份有限公司 | Method for purifying natural lycopene |
| CN106174165A (en) * | 2016-06-27 | 2016-12-07 | 徐州工程学院 | A kind of short flash extracting method of lycopene |
| CN110613132A (en) * | 2019-10-14 | 2019-12-27 | 广州市康伦生物技术有限公司 | Preparation method of high cis-lycopene-containing microcapsule |
| CN114259051A (en) * | 2021-12-31 | 2022-04-01 | 新疆中基天然植物纯化高新技术研究院有限公司 | Method for rapidly preparing lycopene |
-
2002
- 2002-10-22 CN CNB021465606A patent/CN1176159C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315953C (en) * | 2003-09-15 | 2007-05-16 | 广州优宝工业有限公司 | Preparation method of lycopene |
| CN1965693B (en) * | 2006-06-13 | 2012-12-05 | 新疆屯河投资股份有限公司 | Method for purifying natural lycopene |
| CN106174165A (en) * | 2016-06-27 | 2016-12-07 | 徐州工程学院 | A kind of short flash extracting method of lycopene |
| CN110613132A (en) * | 2019-10-14 | 2019-12-27 | 广州市康伦生物技术有限公司 | Preparation method of high cis-lycopene-containing microcapsule |
| CN114259051A (en) * | 2021-12-31 | 2022-04-01 | 新疆中基天然植物纯化高新技术研究院有限公司 | Method for rapidly preparing lycopene |
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