CN1556150A - Extraction, separation and preparation method of procyanidin and its derivatives - Google Patents
Extraction, separation and preparation method of procyanidin and its derivatives Download PDFInfo
- Publication number
- CN1556150A CN1556150A CNA2004100216500A CN200410021650A CN1556150A CN 1556150 A CN1556150 A CN 1556150A CN A2004100216500 A CNA2004100216500 A CN A2004100216500A CN 200410021650 A CN200410021650 A CN 200410021650A CN 1556150 A CN1556150 A CN 1556150A
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- former
- carthamin
- extraction
- solvent
- preparation
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- 238000000926 separation method Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims description 23
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- MOJZMWJRUKIQGL-FWCKPOPSSA-N Procyanidin C2 Natural products O[C@@H]1[C@@H](c2cc(O)c(O)cc2)Oc2c([C@H]3[C@H](O)[C@@H](c4cc(O)c(O)cc4)Oc4c3c(O)cc(O)c4)c(O)cc(O)c2[C@@H]1c1c(O)cc(O)c2c1O[C@@H]([C@H](O)C2)c1cc(O)c(O)cc1 MOJZMWJRUKIQGL-FWCKPOPSSA-N 0.000 title abstract 6
- HGVVOUNEGQIPMS-UHFFFAOYSA-N procyanidin Chemical compound O1C2=CC(O)=CC(O)=C2C(O)C(O)C1(C=1C=C(O)C(O)=CC=1)OC1CC2=C(O)C=C(O)C=C2OC1C1=CC=C(O)C(O)=C1 HGVVOUNEGQIPMS-UHFFFAOYSA-N 0.000 title abstract 6
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- TUJPOVKMHCLXEL-UHFFFAOYSA-N eriodictyol Natural products C1C(=O)C2=CC(O)=CC(O)=C2OC1C1=CC=C(O)C(O)=C1 TUJPOVKMHCLXEL-UHFFFAOYSA-N 0.000 description 1
- 235000011797 eriodictyol Nutrition 0.000 description 1
- SBHXYTNGIZCORC-UHFFFAOYSA-N eriodyctiol Natural products O1C2=CC(O)=CC(O)=C2C(=O)CC1C1=CC=C(O)C(O)=C1 SBHXYTNGIZCORC-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- 238000011835 investigation Methods 0.000 description 1
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- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002366 mineral element Substances 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
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- 231100000957 no side effect Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
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- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
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- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
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Images
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- Cosmetics (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
本发明公开了一种原花红色素的提取、分离及其衍生物的制备方法。其特点是采用落叶松树皮作原料，自然风干，经粉碎粒径为1～15mm，筛分除去杂质，将溶剂浓度5～95％的水溶液，按物料∶溶剂＝1∶8～40加入提取罐中，于温度30～80℃，常压回流提取1～8小时或减压强制循环提取1～4小时或逆流提取4～6次，然后减压浓缩回收提取溶剂，产物经过滤后，用萃取溶剂脱除树脂和树胶等杂质，获得原花红色素粗产品。再经分离纯化获得原花红色素E、原花红色素C、原花红色素W和原花红色素衍生物，即原花红色素A。该色素适用于不同食品、果酒、饮料和水果罐头以及化妆品等着色，有显著的经济效益和社会效益。
The invention discloses a method for the extraction and separation of proanthocyanidin and its derivatives. It is characterized in that larch bark is used as raw material, air-dried naturally, crushed to a particle size of 1-15mm, sieved to remove impurities, and an aqueous solution with a solvent concentration of 5-95% is added to the extraction tank according to material:solvent=1:8-40 In the process, at a temperature of 30-80°C, extract under normal pressure for 1-8 hours under reflux or under reduced pressure for 1-4 hours or under countercurrent extraction for 4-6 times, and then concentrate under reduced pressure to recover the extraction solvent. After the product is filtered, use the extraction The solvent removes impurities such as resin and gum to obtain the crude product of procyanidin. After separation and purification, procyanidin E, procyanidin C, procyanidin W and procyanidin derivatives, ie, procyanidin A, are obtained. The pigment is suitable for coloring various foods, fruit wines, beverages, canned fruits and cosmetics, and has significant economic and social benefits.
Description
One, technical field
The present invention relates to the preparation method of extraction, separation and the derivative thereof of a kind of former carthamin (Proanthocyanidins Red).The former carthamin product of method acquisition can be used for the hyperchromic of fruit wine, beverage, fruit can, meat-based food and makeup or toning thus.
Two, background technology
Food dye is the important component part of foodstuff additive, and it not only is widely used in beverage, drinks, cake, candy etc. improving its exterior quality, and is applied to medicine and cosmetics production, belongs to fine chemical product.Food dye can be divided into synthetic colour and natural pigment two classes by its source.The food dye that uses at China's approved has 69 kinds (by 1998), wherein combination colour have 21 kinds, natural pigment (majority comes from plant milk extract) has 48 kinds, the application of edible natural pigments such as Li Chuanxin and development trend, " Liaoning agricultural sciences " 2001 (1): 29-32.Along with the progress of synthetic food colors toxicologic study, its safety issue causes extensive concern, and a lot of developed countries are part even all forbid synthetic food colors; In the synthetic colour of present legal use, have at least 5 kinds all to belong to azo-compound, think according to relevant research, this compounds has carcinogenic or potential carcinogenic risk at beta-naphthylamine and the alpha-amino group-1-naphthols that the human body metabolism generates.
Since the seventies in 20th century, the research and development of natural pigment have been become focus again, only Japan is example, and the 70-80 age, disclosed related application was up to 246.Because painted natural, the tone of natural pigment is more near natural goods, safe and nontoxic, side effect, the band trophicity that has or the disposition of supporting one's family, what have has pharmacological effect concurrently, and prophylactic treatment effect, particularly along with the raising of food function and security, natural food colour is subjected to the attention of countries in the world day by day.The natural pigment kind that various countries' approved allows to use increases year by year, and Japan has 102 kinds, and European Union has 26 kinds, and Britain has 26 kinds, and China has 48 kinds (by 1998).
Plant is the main source of natural pigment, according to the literature, the floristics that can extract pigment has hundreds of, raw materials used comprise root, directly, leaf, bark, shell, flower and fruit etc., Lv Huiping. Chinese natural food colour bibliographical reference, " Guangzhou foodstuffs industry science and technology ", 1996 (4) .4.P34-36.Plant pigments generally divides four big classes according to the chemical structure difference: (1) lanaurin is that magnesium ion and pyrrole ring coordination constitute as chlorophyll; (2) polyene pigment is the class pigment that unitary conjugated double bond is connected to the basis with the isoprene residue promptly, as carotenoid; (3) plant polyphenol kind pigment comprises the derivative of polyphenol such as anthocyan, anthoxanthins and poly-proanthocyanidin, as Sorghum pigment, Chrysan Yellow pigment, carthamin, eriodictyol etc., generally has the flavylium ion ketone constructional feature of muttering; (4) ketone, quinochromes promptly contain ketone or quinones structure, comprise Lawsonia inermis, juglone, plumbagin, mango foline etc., Xue Chunqi. and " foodstuff additive ". Beijing: China Light Industry Press, 1991.81-82.Most plant pigmentss are the complex mixtures that are made of the close heterogeneity of chemical structure, have thousands of kinds of structures as Radix Dauci Sativae, and anthocyanin class has more than 200 kind of different structure.
In the above-mentioned natural pigment, the plant polyphenol pigment is the most noticeable, because the color and luster of numerous natural foods and local flavor just have plant polyphenol to participate in formation directly.For example, the formation of the color and luster of tealeaves, coffee, cocoa, grape wine etc., local flavor and hobby etc. just is closely related with it.Simultaneously, plant polyphenol extensively is present in bark, heartwood, leaf and the flowers and fruits of plant, is the secondary metabolite of plant.It and human lives are closely bound up, and people have also taken in polyphenol more or less when edible grain, vegetables, fruit etc.Eighties of last century is since the fifties, reactive behavior mechanism progress of research along with plant polyphenol and protein, polysaccharide, alkaloid, microorganism, enzyme, metal ion etc., anti-oxidant significantly along with it, remove biological activitys such as free radical, inhibitory anti-virus, reducing blood-fat by a large amount of experiment confirms, this class natural product is deep day by day at area researches such as herbal pharmaceutical, functional food and additive, daily chemical products, use very extensive, the green Di Ying of stone. " plant polyphenol ". Science Press, 2000, P.1-4.For this reason, there is viewpoint to think that plant polyphenol is " the 5th nutrient substance " after sugar, fat, protein, mineral element and VITAMIN.
In the plant polyphenol pigment, cyanidin(e) and anthocyanin class account for main body.Because of its wide material sources, aboundresources, colour generation type are many, over nearly 20 years to its research of carrying out than system, the exploitation that has forms commodity.According to investigations, cyanidin(e) plant-sourced 27 sections that have an appointment, 73 belong to, and 83 kinds, Annamaryju DS. " Photochemistry " 1997,45 (4): 671-674.Wherein, as roselle calyx red pigment, black soya bean haematochrome, the preparation technology of natural pigments such as Chinese patent CN860030, haw red pigment, prickly-pear cactus haematochrome, mulberry red pigment, eggplant skin pigment, morning glory pigment, Flos Celosiae Cristatae pigment, common perilla haematochrome and the research of product performance have bibliographical information; From Pericarpium Vitis viniferae cyanidin(e), the red sorghum pigment that Pericarpium Vitis viniferae is extracted, Chinese patent CN1031282C, CN1086831A, CN1066860A, CN88102330.2, cowberry haematochrome CN88204879 etc. have many patent documentations or have been used for producing.
But what the present invention relates to makes raw material with bark of dahurian larch, by the method for extraction, separation and derivative preparation thereof, has obtained former carthamin, yet there are no bibliographical information.
Three, summary of the invention
The objective of the invention is to provide a kind of preparation method of extraction, separation and derivative thereof of former carthamin at the deficiencies in the prior art, being characterized in adopting the abundant bark of dahurian larch of natural red cellulose content is raw material, obtains different former carthamin products such as purity, solvability by extraction, extraction fractionation; By chemical reaction, the preparation suitability is strong, the better former premium derivative dye product of performance again.
Purpose of the present invention is realized that by following technical measures wherein said umber is parts by weight except that specified otherwise.
The preparation method of the extraction of former carthamin, separation and derivative thereof:
1. the preparation of the thick product of former carthamin
Adopt tamarack (Larix gmelini) bark to make raw material, natural air drying, can be adopted as 1～15mm without pulverizing or being crushed to particle diameter, remove impurity through screening, press material: the part by weight that extracts solvent=1: 8～40 adds in the extractor, can soak at normal temperatures earlier 6-12 hour or extract without soaking directly, extract 30～80 ℃ of temperature, atmospheric pressure reflux was extracted 1～6 hour; Or decompression pump circulation extraction 1～4 hour; Or countercurrent extraction 4～6 times, concentrating under reduced pressure reclaims and removes to extract solvent then, and product is through after the coarse filtration, use extraction solvent, impurity such as deresinate, natural gum obtain former carthamin extracting solution, or obtain the sorrel powder, promptly former carthamin crude product (LPR) through super-dry.
2. the separation and purification of former carthamin
With above-mentioned former carthamin extracting solution, press extracting solution: the volume ratio of extraction solvent=1: 1 adds in the extraction container, concussion or stir, aqueous phase is separated out throw out, after filtration, and gained insolubles drying, pulverizing obtains being soluble in the sorrel powder of alcohol, is former carthamin E (LPR-E).Above-mentioned filtrate obtains extraction phase solvent layer and extracting phase water layer respectively by standing demix, and the latter is again with above-mentioned extraction solvent extraction 3-5 time, merge each time extraction phase, adopt concentrating under reduced pressure, reclaim to remove and desolvate, drying, pulverizing obtain red powder, promptly former carthamin C (LPR-C).Remaining extracting phase water layer, drying, pulverizing obtain orange-yellow water colo(u)r, promptly former carthamin W (LPR-W).
3. the preparation of the derivative of former carthamin
With 1 part of above-mentioned former carthamin extracting solution, add 4～6 parts of ethanol: concentrated hydrochloric acid=-95: the solution of 5 volume ratios, add 0～0.2 part of concentration 2% catalyzer again, in 75～95 ℃ of temperature reaction 20～40 minutes, this reaction made the unit connecting key C of proanthocyanidin molecule
4-C
6, C
4-C
8Fracture generates flavan-3-alcohol and cyanidin(e) unit, obtains being under the acidic conditions proanthocyanidin derivative of hunting pink thus, promptly former carthamin A (LPR-A).
Extract solvent and be hot water and/or can with water with arbitrary proportion blended solvent alcohol and/or ketone.
Extraction solvent is at least a in sherwood oil, light oil, ethyl acetate and/or the ethyl butyrate.
Catalyzer is CoCl
2, CuSO
4, CuCl
2, NH
4Fe (SO
4)
2.12H
2O, MnCl
2Or FeSO
4In any one.
The characteristic and the purposes of former premium natural pigment physics and chemistry
1. the dissolution characteristics of former carthamin is, is soluble in organic solvent and water-containing solvents thereof such as methyl alcohol, ethanol, acetone, propyl alcohol.Be insoluble in ether, oil fan, chloroform, tetracol phenixin, benzene and toluene.Its Central Plains premium E is insoluble in water and ethyl acetate, but is soluble in the ethanol aqueous solution of dehydrated alcohol and any concentration; Former premium C is soluble in ethyl acetate, water soluble; Former premium W and former premium A are soluble in water.
2. the methanol solution of former carthamin has maximum absorption band at the 225nm place, and there is asymmetric absorption peak at the 277nm place, and there is weak mild absorption peak at the 550-577nm place.
3. the look valency E of former carthamin
1% 1cm577nm=284.Be orange when pigment solution concentration is lower than 0.005%, concentration is higher than 0.01%, is bright scarlet.When pH＜2.0, produce muddy, precipitation; PH＞12 o'clock are sorrel; Red stable, transparent under other pH condition.Pigment solution is 100 ℃ of heat treated: pigment was stable in 30 minutes, heat precipitation to occur in 1 hour, heat and became the milkiness shape in 2 hours, the redness disappearance.
4. metal ion is to the influence of former carthamin solution.In the pigment solution of 0.05% concentration, add different metal ionic salt (content is 0.001mol/L) respectively, wherein NaCl, CaCl
2, BaCl
2, MgSO
4Do not have obvious influence Deng to pigment solution, its color and luster, transparency and light absorption value change hardly; Add AlCl
3Can cause the solution muddiness; FeSO
4Make pigment solution become brown, FeCl
3Can cause that pigment produces the chocolate precipitation.
5. the cracking of former carthamin (LPR) generating unit connecting key under acid or base catalysis.For example in alcohol-concentrated hydrochloric acid, a small amount of transition metal such as Co are arranged
2+, Cu
2+, Mn
2+, Fe
2+And Fe
3+When participating in catalysis, the occurrence characteristics cyanidin(e) reacts, and produces the former carthamin A (LPR-A) of hunting pink, and acromion occurs at 450nm.
6. former carthamin is applicable to different foods, and especially fruit wine, beverage, fruit are irritated head and fabric coloring.
The present invention has following advantage:
1. the proanthocyanidin and the derivatization reaction product thereof that derive from bark of dahurian larch are that former carthamin is for mainly being colour content, it is similar to contained pigment main components such as grape, black tea, red gallon, black currant, raspberry, strawberry, cherries, equal platymiscium polyphenol pigment, chemical homology is arranged, so use its painted more apparent nature.
This natural pigment except that be used for painted, certain physiology live function and trophicity are arranged, can play anti-oxidant, antibacterial, remove free radical, and effect such as expansion capillary vessel, have similar vitamin P effect.
3. LPR-E is that pure dissolubility is applicable to fruit cans such as fruit wine, grape wine, cherry and strawberry in such pigment; LPR-A is applicable to acidic juice beverage, black tea drinks and cold drink food.LPR-C has certain fat-soluble fat-containing food that can be used for, and is a kind of natural red colouring matter that safely, has no side effect.
4. this natural pigment and natural protein fiber, plant cellulose, materials with hide glue fibril, nylon 6, PVP, poly-
Vinyl alcohol can be used for fabric coloring in conjunction with firmly.Also can be by itself and the complex reaction of metal ion raising tinting strength, enhanced stability is widened color range.
Four, description of drawings
Fig. 1. the molecular structure of the natural main color composition of former premium and colour generation schematic diagram;
Fig. 2. the extraction and separation process schema of former premium natural pigment;
Fig. 3. the reaction mechanism synoptic diagram of former premium natural pigment derivative (is example with cyanidin B-2).
Five, embodiment
Below by concrete example the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the personnel that are skilled in technique in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1:
The first step: the preparation of former carthamin crude product
Select for use tamarack (Larix gmelini) bark of natural air drying to make raw material, pulverize particle, remove impurity through screening into the about 1-15mm of particle diameter.Take by weighing the 10Kg above-mentioned raw materials, add 75% aqueous acetone solution 80L, in the vacuum return tank, in 35 ± 5 ℃ of temperature, atmospheric pressure reflux was extracted 8 hours, discharging.By coarse filtration, go out the material slag, obtain filtrate, filtrate is drawn in the vacuum return tank, concentrating under reduced pressure reclaims acetone, and discharging is put into the extractor cool to room temperature to feed liquid.Add petroleum ether extraction then, deresinate and natural gum.Obtain former carthamin extracting solution thus, or spray-dried pigment crude product (LPR) 1.76Kg, the productive rate about 18% of getting.The molecular structure of former carthamin main component and colour generation principle are as shown in Figure 1.
Second step: the separation and purification of former carthamin
Get the former carthamin extracting solution of above-mentioned gained 15L, press extracting solution: the volume ratio of ethyl acetate=1: 1 adds ethyl acetate 15L, concussion, aqueous phase is separated out throw out, after filtration, the gained insolubles adopts vacuum-drying, pulverizing obtains being soluble in the sorrel powder 837g of alcohol, is former carthamin E (LPR-E).Above-mentioned filtrate is passed through standing demix, obtain extraction phase ethyl acetate layer and extracting phase water layer respectively, the latter uses ethyl acetate extraction 3 times again, merge each time extraction liquid, adopt concentrating under reduced pressure, reclaim earlier and remove ethyl acetate, vacuum-drying again, pulverize and obtain fat-soluble red powder 440g, promptly former carthamin C (LPR-C).Remaining extracting phase (water layer) through spraying drying, is pulverized and is obtained orange-yellow water colo(u)r 480g, promptly former carthamin W (LPR-W), and the ratio of above-mentioned three kinds of pigments is respectively approximately: 47.64%, 25.04%, 27.32%.Technical process is seen shown in Figure 2.
The 3rd step: the derivative reaction of former carthamin
Get above-mentioned former carthamin extracting solution 1L, add 6L ethanol: the solution of the volume ratio of concentrated hydrochloric acid=95: 5 adds 0.2L concentration and is 2% NH again
4Fe (SO
4)
2.12H
2The cyanidin(e) reaction 95 ℃ of heated and stirred reactions of temperature 40 minutes, takes place, the unit connecting key C of feasible poly-proanthocyanidin in the O aqueous solution
4-C
6, C
4-C
8Fracture generates flavan-3-alcohol and cyanidin(e) unit, forms the pigment that acidic conditions is hunting pink, promptly former carthamin derivative A (LPR-A).Its transformation efficiency reaches more than 50%.
The first step: the preparation of former carthamin crude product
With natural air drying, do not make raw material through tamarack (Larix gmelini) the bark piece of pulverizing, remove impurity through screening, take by weighing above-mentioned raw materials 15Kg, the ethanol 50L of adding 95% at room temperature soaked 8-12 hour, moved into subsequently in the multifunctional stainless steel extractor, add the above-mentioned ethanolic soln of 100L again, 75 ± 5 ℃ of temperature, start recycle pump, forced refluence extracted 2 hours, discharge filtrate subsequently, and collect.And then in extractor, add the above-mentioned ethanolic soln of 100L, and to extract 1 hour by above-mentioned technology, discharging is also collected filtrate.Then get rid of in the jar and expect slag, clean up extractor, merge the filtrate of twice gained subsequently, pump in the multi-function extractor, at 35 ± 5 ℃ of following decompression and solvent recoveries of temperature.Emit liquid, after coarse filtration, obtain former carthamin extracting solution, get pigment crude product (LPR) 2.2Kg, productive rate about 14.7% by spraying drying again.
Second step: the separation and purification of former carthamin
Get the described former carthamin extracting solution 15L of the first step, press extracting solution: the volume ratio of ethyl acetate=1: 1 adds ethyl acetate 15L, concussion, aqueous phase is separated out throw out, after filtration, the gained insolubles adopts vacuum-drying, pulverizing obtains being soluble in the sorrel powder 703g of alcohol, is former carthamin E (LPR-E).Above-mentioned filtrate is passed through standing demix, obtain extraction phase ethyl acetate layer and extracting phase water layer respectively, the latter uses ethyl acetate extraction 5 times again, merge each time extraction phase, adopt concentrating under reduced pressure, reclaim earlier and remove ethyl acetate, vacuum-drying again, pulverize and obtain fat-soluble red powder 492g, promptly former carthamin C (LPR-C).Remaining extracting phase water layer through spraying drying, is pulverized and is obtained orange-yellow water colo(u)r 476g, promptly former carthamin W (LPR-W), and the yield of above-mentioned three kinds of pigments is respectively approximately: 42.07%, 29.44%, 28.49%.
The 3rd step: the preparation of the derivative of proanthocyanidin
Get above-mentioned former carthamin extracting solution 1L, add 6L ethanol: the solution of concentrated hydrochloric acid=90: 5 volume ratio at whipped state, feeds O
2, in water-bath, be heated to 85 ℃ of reactions 20 minutes.The reaction of generation cyanidin(e), the unit connecting key C of feasible poly-proanthocyanidin
4-C
6, C
4-C
8Fracture generates flavan-3-alcohol and cyanidin(e) unit, forms the pigment that acidic conditions is hunting pink, former carthamin derivative A (LPR-A).Its transformation efficiency reaches 63%.
Embodiment 3
The first step: the preparation of former carthamin crude product
With natural air drying, do not make raw material through tamarack (Larix gmelini) the bark piece of pulverizing, remove impurity through screening, take by weighing four parts of above-mentioned raw materials, every part of 10Kg moves into respectively in the stainless steel extractors such as No. 1, No. 2, No. 3 and No. 4, makes extraction agent with 80 ℃ of hot water, adopt countercurrent extraction, material extracts through 4 times in every jar.By single jar of calculating, each add-on is 200L, total material: hot water=1: 80, under 80 ℃ of temperature, start whipping appts, and extracted totally 4 hours 1 hour at every turn.Discharge feed liquid subsequently, concentrating under reduced pressure in the triple effect thickener, discharging after coarse filtration, is put into the extractor cool to room temperature to feed liquid, adds light oil concussion then or stirs, treat standing demix after, deresinate and natural gum.Obtain former carthamin extracting solution, again by dry pigment crude product (LPR) 1.46Kg, the productive rate about 14.6% of getting.
Second step: the separation and purification of former carthamin
Get the described former carthamin extracting solution 50L of the first step, press extracting solution: the solution of ethyl acetate=1: 1 volume ratio, add ethyl acetate 50L, concussion, aqueous phase is separated out throw out, after filtration, the gained insolubles, adopt vacuum-drying, pulverize the sorrel powder 607.4g that obtains being soluble in alcohol, be the former premium E of natural pigment (LPR-E).Above-mentioned filtrate is passed through standing demix, obtain extraction phase ethyl acetate layer and extracting phase water layer respectively, the latter uses ethyl acetate extraction 6 times again, merge each time extraction phase, adopt concentrating under reduced pressure, reclaim earlier and remove ethyl acetate, vacuum-drying again, pulverize and obtain fat-soluble red powder 392.7g, promptly former premium C (LPR-C).Remaining extracting phase (water layer) through spraying drying, is pulverized and is obtained orange-yellow water colo(u)r 459.9g, promptly former premium W (LPR-W), and the yield of above-mentioned three kinds of pigments is respectively approximately: 41.6%, 26.9%, 31.5%.
The 3rd step: the preparation of the derivative of proanthocyanidin
Get above-mentioned former carthamin extracting solution 2L, add 8L ethanol: the solution of concentrated hydrochloric acid=95: 5 volume ratio adds 0.2L concentration and is 2% CuCl again
2The aqueous solution is heated to 75 ℃ of reactions 60 minutes as catalyzer in water-bath.The reaction of generation cyanidin(e), the unit connecting key C of feasible poly-proanthocyanidin
4-C
6, C
4-C
8Fracture generates flavan-3-alcohol and cyanidin(e) unit, forms the pigment that acidic conditions is hunting pink, former premium natural pigment derivative (LPR-A).Its transformation efficiency reaches 58%.
Application example
1, using former carthamin C mixes colours to red bayberry fruit wine
Get the former fruit wine of red bayberry and add the former carthamin C toning of 0.3-0.5% respectively, allotments such as spices, membrane filtration, sterilization, finished product.This wine is shallow Ruby red, and color and luster is pleased the people, and the smell of fruits is very sweet, the aroma strong fragrance, drink soft mellow, and aftertaste is long.
2, the former carthamin E of application is hyperchromic to canned cherry
Get former carthamin E and be made into 2% pigment solution with the dissolving of 5% edible ethanol, the bright cherry of will be through despecking, cleaning, draining is put into pigment solution and is soaked about 30min, drain subsequently, pack in the clean Cans, add liquid glucose, then sealed cans, send into Sterilization Kettle sterilization 30min, cooling, check, packing.
3, using former carthamin A mixes colours to iced black tea
2000ml is an example with the allotment iced black tea, get black tea concentrated solution 8-10ml (or getting instant black tea powder 2.6g), stir with warm water dissolving adding preparation and 50% good syrup 400ml of purification, take by weighing citric acid 3.6g, oxysuccinic acid 0.8g, Trisodium Citrate 1.2g, slowly pour in the tea after the former carthamin A of 1.0g fully dissolved with small amount of ethanol, the limit bevelling stirs, after adding water to 2000mlc again and stirring, use sand rod suction filtration, be heated to 80 ℃, add iced black tea essence 2.0ml, lemon flavour 1.4ml, post-heating to 90 ℃ stirs, make the pH value be 2.8-3.2, be filled into while hot in the heat-resisting PET bottle that the hydrogen peroxide sterilization is cleaned, be inverted immediately behind the screw capping.
4, the former carthamin C of application is painted to the black tea ice-creams
Add former carthamin C 0.3% in following ratio, black tea concentrated solution 0.8%-1.4%, or 0.25g% instant black tea powder, white sugar 10%, sodium carboxymethylcellulose pyce and gelatin add water heating to make massfraction are 10% solution, and starch 2.5% adds water furnishing starch slurry.Under agitation fresh milk 1%, egg slurry, white sugar, gelatin, Xylo-Mucine, starch slurry and tea Normal juice and pigment are joined thorough mixing in the feed liquid mixing tank.
Account for 0.2% ratio acid adjustment then with citric acid, feed liquid color under sour environment is more gorgeous, and is the most bright-coloured pleasing when pH＜3.Dark rose ice-creams color is tempting, and is refreshing sweet good to eat; The pink ice-creams delicate mouthfeel in pH＜4.5, milk is strong, by people are liked.
Operations such as follow-up sterilization, homogeneous, feed liquid wear out, quick-frozen shaping technology are routinely carried out.
5, using former carthamin replaces Sodium Nitrite to cook the meat pigment.
Prescription: the prescription of ham sausage adds (1) ratio in the 10Kg raw meat and presses refined salt 3.6%, different Vc sodium 0.06%, pyrophosphate salt 0.15%, niacinamide 0.15%, carrageenin 0.5%, glucose 4%, monosodium glutamate 0.10%, former carthamin 0.015%, frozen water 25%.(2) in addition with white pepper powder 02%, pork essence 0.3% adds 0.15Kg water furnishing emulsus.(3) take by weighing yam starch 0.48Kg again.
The production method of above-mentioned example is production process operation routinely.
Claims (4)
1. the preparation method of former carthamin is characterized in that:
(1) preparation of former carthamin
Adopt bark of dahurian larch to make raw material, natural air drying, can be 1～15mm without pulverizing or through powder particle diameter, impurity is removed in screening, with solvent strength is the aqueous solution of 5～95wt%, press material: the weight ratio of solution=1: 8～40 adds in the extractor, in 30～80 ℃ of temperature, atmospheric pressure reflux extraction 1～8 hour or decompression pump circulation extraction 1～4 hour or countercurrent extraction 4～6 times, concentrating under reduced pressure reclaims and extracts solvent then, product after filtering, with extraction solvent deresinate and gummy impurity, obtain former carthamin extracting solution, or drying obtains the brown red powder, it is the thick product of former carthamin
(2) separation and purification of former carthamin
With above-mentioned former carthamin extracting solution, press extracting solution: the volume ratio of extraction solvent=1: 1 adds in the extraction container, concussion or stir, after leaving standstill, aqueous phase is separated out throw out, after filtration, gained insolubles drying is pulverized the sorrel powder that obtains being soluble in alcohol, is former carthamin E; Above-mentioned filtrate obtains extraction phase solvent layer and extracting phase water layer respectively by standing demix, and the latter with extraction solvent extraction 3-5 time, merges each time extraction phase again, adopts concentrating under reduced pressure to reclaim solvent, and drying, pulverizing obtain red powder, promptly former premium C; Extracting phase, drying is pulverized, and obtains orange-yellow water colo(u)r, promptly former carthamin W,
(3) preparation of former carthamin derivative
With 1 part of above-mentioned former carthamin extracting solution, add 4～6 parts of ethanol: concentrated hydrochloric acid=95: 5, the solution of volume ratio, adding 0～0.2 part of concentration again is 2% catalyzer, in 75～95 ℃ of temperature reaction 20～60 minutes, this reaction made the unit connecting key C of proanthocyanidin molecule
4-C
6, C
4-C
8Fracture generates flavan-3-alcohol and cyanidin(e) unit, obtains being under the acidic conditions proanthocyanidin derivative thing of hunting pink thus, promptly former carthamin A.
2. the preparation method of former carthamin according to claim 1, it is characterized in that extracting solvent and be hot water and/or can with water with arbitrary proportion blended solvent alcohol and/or ketone.
3. the preparation method of former carthamin according to claim 1 is characterized in that extraction solvent is at least a in oil fan, light oil, ethyl acetate and/or the ethyl butyrate.
4. the preparation method of former carthamin according to claim 1, the preparation catalyzer that it is characterized in that former carthamin derivative is CoCl
2, CuSO
4, MnCl
2, NH
4Fe (SO
4)
2.12H
2O, FeSO
4, CuCl
2In any.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101885925A (en) * | 2010-07-01 | 2010-11-17 | 韩山师范学院 | A method for extracting brown pigment from camellia oleifera husk |
| CN102323378A (en) * | 2011-08-29 | 2012-01-18 | 湖南科技大学 | Method for rapidly detecting proanthocyanidin in plant |
| CN102746706A (en) * | 2012-07-31 | 2012-10-24 | 新疆林科院经济林研究所 | Preparation method and application of Korean pine bark natural dye |
| CN103044956A (en) * | 2012-12-14 | 2013-04-17 | 北京林业大学 | Method for extracting natural haematochrome from larch bark |
| CN103450701A (en) * | 2013-09-05 | 2013-12-18 | 青海大学 | Natural dyestuff sensitizer on plateau for dye-sensitized solar cell |
| CN104225956A (en) * | 2014-09-27 | 2014-12-24 | 安徽金禾实业股份有限公司 | Forced circulating extraction method in production of acesulfame |
| CN106343321A (en) * | 2015-12-02 | 2017-01-25 | 武汉绿孚生物工程有限责任公司 | Method for preparing clarified aftertaste-free purple sweet potato anthocyanin concentrated juice |
| CN117924962A (en) * | 2023-12-15 | 2024-04-26 | 江西丹霞生物科技股份有限公司 | A preparation process of grape skin red and its product |
| GB2639058A (en) * | 2024-06-20 | 2025-09-10 | Sages London Ltd | Natural dyes |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4698360B1 (en) * | 1985-04-09 | 1997-11-04 | D Investigations Pharmacologiq | Plant extract with a proanthocyanidins content as therapeutic agent having radical scavenger effect and use thereof |
| EP0840770A4 (en) * | 1996-05-23 | 2002-03-20 | Ian Alexander Gilmour | Process for extraction of proanthocyanidins from botanical material |
| CN1276088C (en) * | 1999-04-23 | 2006-09-20 | 协和发酵工业株式会社 | Method for purifying raw anthocyanidin oligomer |
| CN1100097C (en) * | 1999-05-17 | 2003-01-29 | 中国科学院华南植物研究所 | Process for preparing proanthocyandin |
| CN1176919C (en) * | 2003-03-07 | 2004-11-24 | 桂林莱茵生物制品有限公司 | A method for separating and extracting pine bark oligomer proanthocyanidins |
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| CN101885925A (en) * | 2010-07-01 | 2010-11-17 | 韩山师范学院 | A method for extracting brown pigment from camellia oleifera husk |
| CN101885925B (en) * | 2010-07-01 | 2013-05-15 | 韩山师范学院 | A method for extracting brown pigment from camellia oleifera husk |
| CN102323378A (en) * | 2011-08-29 | 2012-01-18 | 湖南科技大学 | Method for rapidly detecting proanthocyanidin in plant |
| CN102746706A (en) * | 2012-07-31 | 2012-10-24 | 新疆林科院经济林研究所 | Preparation method and application of Korean pine bark natural dye |
| CN103044956A (en) * | 2012-12-14 | 2013-04-17 | 北京林业大学 | Method for extracting natural haematochrome from larch bark |
| CN103450701A (en) * | 2013-09-05 | 2013-12-18 | 青海大学 | Natural dyestuff sensitizer on plateau for dye-sensitized solar cell |
| CN104225956A (en) * | 2014-09-27 | 2014-12-24 | 安徽金禾实业股份有限公司 | Forced circulating extraction method in production of acesulfame |
| CN104225956B (en) * | 2014-09-27 | 2016-09-14 | 安徽金禾实业股份有限公司 | Forced circulation extracting process in acesulfame potassium production |
| CN106343321A (en) * | 2015-12-02 | 2017-01-25 | 武汉绿孚生物工程有限责任公司 | Method for preparing clarified aftertaste-free purple sweet potato anthocyanin concentrated juice |
| CN106343321B (en) * | 2015-12-02 | 2020-01-21 | 武汉绿孚生物工程有限责任公司 | Preparation method of clarified and odorless purple sweet potato anthocyanin concentrated juice |
| CN117924962A (en) * | 2023-12-15 | 2024-04-26 | 江西丹霞生物科技股份有限公司 | A preparation process of grape skin red and its product |
| GB2639058A (en) * | 2024-06-20 | 2025-09-10 | Sages London Ltd | Natural dyes |
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Assignee: Guangzhou Houdy cosmeticesco Co., Ltd. Assignor: Sichuan University Contract fulfillment period: 2007.3.16 to 2012.3.16 contract change Contract record no.: 2009440001523 Denomination of invention: Extraction and separation of proto flower haematochrome and preparation method of its derivatives Granted publication date: 20070307 License type: Exclusive license Record date: 2009.10.9 |
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