CN101747401A - Novel method for preparing high-purity tea saponin - Google Patents
Novel method for preparing high-purity tea saponin Download PDFInfo
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- CN101747401A CN101747401A CN200910157171A CN200910157171A CN101747401A CN 101747401 A CN101747401 A CN 101747401A CN 200910157171 A CN200910157171 A CN 200910157171A CN 200910157171 A CN200910157171 A CN 200910157171A CN 101747401 A CN101747401 A CN 101747401A
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Abstract
The invention provides a novel method for preparing high-purity tea saponin, which belongs to the field of deep processing of agricultural/forestry byproducts. The process can efficiently remove pigment-type components with strong color generation property in tea saponin crude products. The method adopts a technical scheme of complexing the pigment-type components dissolved in water saturated n-butanol through metal ions, utilizing the distribution characteristic of tea saponin in an alkaline water-saturated n-butanol extraction-phase system to distribute and extract tea saponin, collecting and concentrating top phase to be dry, obtaining the tea saponin crude products of which the content is more than or equal to 85 percent, dissolving the obtained D280 macroporous resin product to be aqueous solution in a certain concentration, passing the obtained product through D280 macroporous resin, collecting filtrate, drying the obtained product and obtaining greyish white dry tea saponin (of which the content is more than or equal to 90 percent). The method can be adopted to easily and efficiently prepare high-purity good-color tea saponin products from tea seed cakes or dry tea saponin crude products.
Description
Technical field
The present invention relates to a kind of novel preparation method of high-purity tea saponin, belong to farming, secondary product of forestry deep processing field.
Background technology
Oil tea (C.Oleifera Abel.) belongs to Theaceae (Theacea) Camellia (Camellia) plant, is perennial woody oleiferous plants crop.Mainly be distributed in Zhejiang, Anhui, Fujian, Jiangxi, Henan, Hubei, Hunan, Guangdong, Guangxi, in Huaihe River, on the south the Changjiang river the low mountains and hills area of 14 provinces (district, city), and do not strive ground with grain and cotton, development potentiality is very huge, can effectively alleviate present edible oil supply pressure and arable land tension pressure.In addition, the data of State Statistics Bureau in 2007 show, about 1,000,000 tons of China's tea seed output, wherein Hunan, Jiangxi provinces proportion maximum, about 65%; Secondly be Guangxi, Fujian, Guangdong, Zhejiang and Anhui are respectively 11.8%, 6.9%, 3.2%, 3.5%, 2.4%.
The content of total saponins is higher in the tea seed, accounts for 12% mass fraction.Studies show that Sasanguasaponin (Fig. 1) has strong polarity, and is soluble in water, has pharmacological actions such as anti-inflammatory, impermeabilisation simultaneously.The HLB of theasaponin (hydrophilic-lipophilic balance) value is suitable for the solubilizing agent as washing composition and oil-in-water-type 14～16; And in water, form O/W type micella, have good emulsifying, dispersion, foaming, function such as moistening, it is a kind of vegitabilia's " green " non-ionic type natural surface active agent of excellent property, neither stimulate human body skin, it is also free from environmental pollution,, can be widely used in washing, wool spinning, knitting, medical, industries such as daily-use chemical industry.
The most important target of cosmetics production producer is to produce the product that gets consumer reception.Except that odor type, the aesthetic feeling of product (transparency of opaque products, the nacreous lustre of opaque product, color, the skin sense when smearing and the denseness of product) is also quite important.The present theasaponin product produced of China, mainly be with water carry or alcohol extracting after concentrate and spraying drying and light yellow powdery theasaponin, total saponin content is about 50%, all the other compositions comprise the water-soluble look glycosides that is difficult to remove.This type of theasaponin crude product is applied to daily product, for example washes the reason shampoo, detergent, although scourability is good, the product color of preparation presents dun, and applies to fabric washing and have the staining problem, do not approved, thereby influenced the application of theasaponin in this field by market.
The most important target of cosmetics production producer is to produce the product that gets consumer reception.Except that odor type, the aesthetic feeling of product (transparency of opaque products, the nacreous lustre of opaque product, color, the skin sense when smearing and the denseness of product) is also quite important.The present theasaponin product produced of China, mainly be with water carry or alcohol extracting after concentrate and spraying drying and light yellow powdery theasaponin, total saponin content is about 50%, all the other compositions comprise the water-soluble look glycosides that is difficult to remove.This type of theasaponin crude product is applied to daily product, for example washes the reason shampoo, detergent, although scourability is good, the product color of preparation presents dun, and applies to fabric washing and have the staining problem, do not approved, thereby influenced the application of theasaponin in this field by market.
Therefore, the look glycosides in the removal theasaponin has become the research focus in this field.In recent years, because the development of polymeric adsorbent class material is very fast, the application in natural product extraction is separated is also more and more wider.Relevant scholar also is applied to the polymeric adsorbent of inhomogeneity model separation and purification (" Dalian Polytechnic University's journal of theasaponin in the tea seed cake by experiment, 2009,28 (2): 84-86 ", " chemical industry and engineering, 2008,25 (4): 373-376 ", " Chinese oil, 2006,31 (3): 43-45 ", " grain and foodstuffs industry, 2008,15 (2): 27-30 "), but because the molecular polarity similarity of look glycoside composition in the tea waste and theasaponin is big, also adsorbed look glycoside composition in the time of the polymeric adsorbent enrichment theasaponin selected for use in a large number, also be difficult to selective removal during wash-out,, improved the purity of theasaponin though removed partial impurities to a certain extent.So follow-up purifying is often further made with extra care with acetone precipitation, and this method yield is low, the amount of expending is big.
The hydrogen peroxide of lower concentration can oxidative degradation part look glycoside composition (" amino acid and Biological resources, 2006,28 (4): 36-38 ", " grain and grease, 2004,12:26-27 ", " Chinese oil, 2003,28 (4): 42-45 ", " grain and oil processing, 2009,6:71-73 "), but need heat treated, increased energy consumption; This breadboard studies show that (data are not delivered) of while, for theasaponin aqueous solution mass fraction 5% when above, the decolorizing effect of the hydrogen peroxide of lower concentration is unsatisfactory, when the concentration of hydrogen peroxide reaches 15% left and right sides, be just oxidized destruction of sorrel look glycosides composition, solution after the decolouring is pale yellow, but because the oxidisability of hydrogen peroxide makes that hydrophilic sugar chain structure is damaged in the theasaponin, thereby influence the whipability of theasaponin and follow-up product application, and the existence of hydrogen peroxide has also increased potential safety hazard.
Chinese patent CN101270142A discloses " preparation method of Sasanguasaponin " this method and has made the solvent extraction theasaponin with acetone-water, use macroporous resin D101 simultaneously the theasaponin of slightly carrying is carried out enrichment, after the alcoholic solution wash-out is collected, adopt the processing of decolouring of D941 macroporous resin once more.Though this technology only needs two-step purifying, exist the time of obtaining product longer.And the acetone that adopts when extracting is the inflammable volatile kind solvent of lower boiling.
In view of China's tea seed (tea seed (Camellia oleifera Abel.) and camellia seed (Camellia sinesis L. (O) .Kzte)) aboundresources, effectively enrichment prepares high-purity tea saponin, enlarge the Application Areas of theasaponin, for the standard of living that improves people, local peasant has remarkable social benefit with affluence.
Summary of the invention
In order to overcome above-mentioned shortcoming, the technical solution adopted in the present invention is: 1. directly be raw material with the tea seed cake.Salt or alkaline reagents are added in the distribution extraction system of the thick water lift solution of water saturated propyl carbinol-theasaponin, change pigment and theasaponin about conventional allocation coefficient in the two-phase (in making that theasaponin more and being enriched in mutually, be dissolved in down in the phase aqueous solution and the pigment composition), jolting, behind the standing demix, isolate phase, and the pigment constituents is carried out complexing (having increased the solubleness of look glycoside composition in the phase aqueous solution down) at the last certain mass fractional metal ion that adds in mutually, again with isolated down after the aqueous solution carries out the jolting layering mutually, in the collection mutually and be concentrated into do after, be certain mass concentration with water dissolution, dynamically carry out the essence decolouring by the D280 macroporous resin, collect filtrate, get high-purity tea saponin after the drying; 2. be raw material with dry state theasaponin crude product.Dissolve with water-saturated n-butanol earlier, after adding behind the metal ion of certain mass concentration the salt brine solution jolting layering with meta-alkalescence again, in the collection mutually and be concentrated into do after, be certain mass concentration with water dissolution, dynamically carry out the essence decolouring by the D280 macroporous resin, collect filtrate, get the liquid concentration drying after high-purity tea saponin decolours after the drying and be prepared into the high-purity tea saponin product.Because the propyl carbinol recyclability is good, reduced product cost, and propyl carbinol is nonflammable, toxicity is low.And used resin mainly is that the pigment in the product is removed in enrichment, thereby reduced preparation time and cost.
Wherein, described salt or alkaline reagents be KCL, KAc, NaAc, NaCL, K2SO4, Na2SO4, KHCO3, K2CO3, NaHCO3, Na2CO3, KOH or NaOH etc. a kind of or several, its shared mass fraction≤5%; Described metal ion is a kind of of CaCL2, CaSO4, MgCL2, MgSO4, AlCL3, Al2 (SO4) 3, ZnSO4, CuSO4, CuCL2, FeCL2, FeCL3, FeSO4, Fe2 (SO4) 3 or several, the mass fraction of adding≤3%.The volume ratio of distributing with water saturated propyl carbinol is 1: 1～1: 10, and described specificity macroporous anion exchange resin is D280.
Description of drawings
Fig. 1 is the structural formula figure of Sasanguasaponin;
Fig. 2 be homogenous quantities concentration the theasaponin crude product (on) with the methanol solution of smart decolouring dry back high-purity tea saponin product (descending) in ultraviolet-visible scan light spectrogram;
Fig. 3 is a kind of novel preparation method process flow sheet of high-purity tea saponin.
Embodiment
The concrete technical process of the present invention is:
1), with the tea seed cake after the degreasing and 50 ℃ of tap water or 30%～90% (v/v) aqueous solutions of organic solvent with 1: 5～1: 20 (w/v) { preferred 50% (v/v) ethanolic soln }, supersound extraction 30min under the room temperature, repeat 2 times, the aqueous solution that merges filtered liquid standby (with organic solvent extraction, need low pressure to reclaim organic solvent);
2), the aqueous solution of above-mentioned preparation adds water saturated propyl carbinol (volume ratio is 1: 1～1: 10), adds the salt or the alkaline reagents (mass fraction≤5%) of certain mass umber simultaneously, carries out liquid liquid and distributes extraction;
3), on isolated, add metal ion (mass fraction≤3%) in mutually, again with isolated down after the aqueous solution carries out the jolting layering mutually, separate also collect mutually stand-by;
4), if extracting the preparation of going up phase in the step poly-3 is raw material with dry state theasaponin crude product, then earlier with the water saturated propyl carbinol dissolving of the metal ion (mass fraction≤3%) of certain mass umber theasaponin crude product, again with the salt or the alkaline reagents (mass fraction≤5%) of certain mass umber, carry out liquid liquid and distribute extraction, must go up phase.After reclaiming propyl carbinol under the last phase low pressure, with tap water theasaponin being mixed with 5%～20% (w/v), is D280 with certain flow rate by macroporous anion exchange resin simultaneously;
5), effusive decolouring aqueous solution convection drying in the step poly-4 is prepared into highly purified theasaponin (yield is about 30%).
Further specify the present invention by the following examples, but not limited by embodiment.
With the degreasing tea seed cake is raw material, take by weighing 1kg degreasing tea seed cake, add 5L tap water (50 ℃), behind the supersound extraction 30min, use filtered through gauze, repeat twice, united extraction liquid gets the 7L crude extract, and add 350 yellow soda ash make it the dissolving, after adding the extraction of 21L water-saturated n-butanol simultaneously, on isolated, add the 5g metal-salt in mutually and make it dissolving, once more with isolated down mutually after the jolting layering, on reclaim propyl carbinol under the propyl carbinol phase low pressure of extraction mutually after, it is made into the aqueous solution of about 15% mass fraction, flow velocity with " become can not drip stream " carries out further smart decolouring by the resin column chromatography that column internal diameter 5cm is equipped with D280, and effluent liquid carries out dry the about 70g of theasaponin.
The theasaponin crude product that this example is buied with market (theasaponin content is about 50%) is that purifying is to picture, with water saturated butanol solution 12L dissolving 1kg crude product theasaponin, add the 20g metal-salt simultaneously, and carry out liquid liquid with 4L tap water (yellow soda ash that contains 5% mass fraction) and distribute extraction; On reclaim propyl carbinol under the propyl carbinol phase low pressure of extraction mutually after, it is made into the aqueous solution of about 15% mass fraction, flow velocity with " become can not drip stream " carries out further smart decolouring by the resin column chromatography that column internal diameter 5cm is equipped with D280, and effluent liquid carries out dry the about 200g of theasaponin.
The assay of theasaponin adopts the vitriol oil-vanillin assay.Figure below is the ultraviolet-visible scan light spectrogram of theasaponin crude product and the dried theasaponin product of smart decolouring.
Claims (9)
1. the novel preparation method of a high-purity tea saponin is characterized in that: theasaponin content 〉=90% of extraction and purification gained the tea seed cake after sloughing Residual oil, adopt step as follows:
1) will slough dried tea seed cake behind the Residual oil, stir extraction (repeating 2～3 times) with tap water or certain density organic solvent, filter back (as extraction agent, needing the reclaim under reduced pressure organic solvent) with organic solvent theasaponin coarse filtration liquid;
2) add the salt or the alkaline reagents of certain mass umber in the theasaponin coarse filtration liquid, add the water-saturated n-butanol solution of certain volume after the dissolving again, jolting and standing demix are isolated phase, and last mutually in the Ca of adding certain mass umber
2+, Mg
2+, Al
3+, Zn
2+, Cu
2+Or Fe
2+/
3+Carry out complexing with the pigment composition, go up and jolting and standing demix together mutually down isolated again, get phase and be concentrated into and get content after dried greater than 85% theasaponin sample;
3) with content greater than 85% theasaponin sample, be diluted with water to finite concentration after, dynamically by the D280 macroporous resin, collect filtrate, after the drying canescence and content greater than 90% theasaponin sample.
2. the novel preparation method of a high-purity tea saponin is characterized in that: prepare the theasaponin sample of content 〉=90% from dry state theasaponin crude product, adopt step as follows:
1) with dry state theasaponin dissolving crude product in water saturated butanol solution, add the Ca of certain mass umber simultaneously
2+, Mg
2+, Al
3+, Cu
2+Or Fe
2+/
3+, add the salt of certain mass umber or the aqueous solution of alkaline reagents again, jolting and standing demix, get mutually and be concentrated into after doing content greater than 85% theasaponin sample;
2) with content greater than 85% theasaponin sample, be diluted with water to finite concentration after, dynamically by the D280 macroporous resin, collect filtrate, after the drying canescence and content greater than 90% theasaponin sample.
3. a production method as claimed in claim 1 is characterized in that used tea seed cake raw material is the grouts after camellia seed (Camellia sinesis L. (O) .Kzte) or tea seed (the Camellia oleifera Abel.) oil expression;
4. a production method as claimed in claim 1 is characterized in that used organic solvent is methyl alcohol or ethanol, and concentration is in 40%～95% scope;
5. a production method as claimed in claim 2 is characterized in that theasaponin content is 30～60% in the described dry state theasaponin crude product;
6. a production method as claimed in claim 1 or 2 is characterized in that described salt or alkaline reagents are KCL, KAc, NaAc, NaCL, K
2SO
4, Na
2SO
4, KHCO
3, K
2CO
3, NaHCO
3, Na
2CO
3, KOH or NaOH etc. a kind of or several, its shared mass fraction≤5%;
7. a production method as claimed in claim 1 or 2 is characterized in that described Ca2+, Mg2+, Al3+, Zn2+, Cu2+ or Fe2+/3+ metal ion is CaCL
2, CaSO
4, MgCL
2, MgSO
4, AlCL
3, Al
2(SO
4)
3, ZnSO
4, CuSO
4, CuCL
2, FeCL
2, FeCL
3, FeSO
4, Fe
2(SO
4)
3A kind of or several, the mass fraction of adding≤3%;
8. a production method as claimed in claim 1 or 2 is characterized in that water saturated n-butanol extraction system is the meta-alkalescence system, adds water saturated propyl carbinol volume parts and is 1～10 times of following phase volume of water fractional, and the best is 3 times;
9. a production method as claimed in claim 1 or 2 is characterized in that used macroporous resin is D280.
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| CN2009101571714A CN101747401B (en) | 2009-12-23 | 2009-12-23 | Novel method for preparing high-purity tea saponin |
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|---|---|---|---|
| CN2009101571714A CN101747401B (en) | 2009-12-23 | 2009-12-23 | Novel method for preparing high-purity tea saponin |
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| CN101747401B CN101747401B (en) | 2012-03-28 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030807A (en) * | 2010-10-21 | 2011-04-27 | 华南理工大学 | Theasapogenol derivative with anti-HIV (Human Immunodeficiency Virus) activity, preparation method and application thereof |
| CN102499911A (en) * | 2011-10-25 | 2012-06-20 | 华南理工大学 | Tea saponine nanocapsule, preparation method and application thereof |
| US10660924B2 (en) | 2015-11-25 | 2020-05-26 | Natural Response, S.A. | Method for obtaining saponins from plants |
-
2009
- 2009-12-23 CN CN2009101571714A patent/CN101747401B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030807A (en) * | 2010-10-21 | 2011-04-27 | 华南理工大学 | Theasapogenol derivative with anti-HIV (Human Immunodeficiency Virus) activity, preparation method and application thereof |
| CN102030807B (en) * | 2010-10-21 | 2012-12-05 | 华南理工大学 | Theasapogenol derivative with anti-HIV (Human Immunodeficiency Virus) activity, preparation method and application thereof |
| CN102499911A (en) * | 2011-10-25 | 2012-06-20 | 华南理工大学 | Tea saponine nanocapsule, preparation method and application thereof |
| CN102499911B (en) * | 2011-10-25 | 2013-11-13 | 华南理工大学 | Tea saponine nanocapsule, preparation method and application thereof |
| US10660924B2 (en) | 2015-11-25 | 2020-05-26 | Natural Response, S.A. | Method for obtaining saponins from plants |
| US11510954B2 (en) | 2015-11-25 | 2022-11-29 | Desert King Chile S.A. | Method for obtaining saponins from plants |
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| Publication number | Publication date |
|---|---|
| CN101747401B (en) | 2012-03-28 |
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