CN102180935A - Method for preparing high-purity sasanquasaponins - Google Patents

Method for preparing high-purity sasanquasaponins Download PDF

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Publication number
CN102180935A
CN102180935A CN 201110066908 CN201110066908A CN102180935A CN 102180935 A CN102180935 A CN 102180935A CN 201110066908 CN201110066908 CN 201110066908 CN 201110066908 A CN201110066908 A CN 201110066908A CN 102180935 A CN102180935 A CN 102180935A
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China
Prior art keywords
sasanguasaponin
high purity
oil tea
filter
preparing
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CN 201110066908
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满汉云
满孜孜
满意
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HUNAN HANQING BIOLOGICAL CO Ltd
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HUNAN HANQING BIOLOGICAL CO Ltd
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Priority to CN 201110066908 priority Critical patent/CN102180935A/en
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Abstract

The invention discloses a method for preparing high-purity sasanquasaponins. The method comprises the following steps of: performing ultrasonic counter-current extraction of the sasanqua cakes serving as a raw material or dissolving raw sasanqua saponins serving as a raw material in a solvent, and performing filtration, ionic exchange, macro-porous adsorption, concentration and the like to obtain the high-purity white powdery sasanquasaponins of which the purity is over 95 percent. The high-purity sasanquasaponins can be applied to the high-end fields of foods, pharmacy, electronics, printing and the like. The method has the advantages of meeting national requirements of energy conservation, emission reduction and pollution-free production, realizing mass production, solving the problems of high cost, high energy consumption, difficulty in removing impurities and decolorizing and the like in an industrial sasanquasaponin-purifying method, along with low solvent consumption, low energy consumption and high extraction rate.

Description

A kind of method for preparing the high purity sasanguasaponin
Technical field
The present invention relates to field of fine chemical, specifically is a kind of preparation method of high purity sasanguasaponin.
Background technology
Oil tea (Camellia oleifera Abel), belong to Theaceae (Theaceae) Camellia (CamelliaL.) plant, be evergreen dungarunga or shrub, be the distinctive woody edible oil materials seeds of China, the cultivation in more than 2000 year is arranged and utilize historical, with Fructus oleae europaeae, oil palm, coconut and be called the world four big woody oleiferous plants plants, with Chinese tallow tree, tung oil tree and walnut and be called China four big woody oleiferous plants plants.At present, China's oil tea area has 4,500 ten thousand mu approximately, about 1,000,000 tons of tea seed annual production, produce about 260,000 tons of tea oil per year, about 11,000,000,000 yuan of the output value, mainly be distributed in the Yangtze valley and on the south 14 provinces (city, district), wherein Jiangxi, Hunan, Guangxi San Sheng (district) account for 76.2% of national total area.Tea seed utilizes degree near 100%, 14 the oil tea main products in the whole nation are economized (district, city) 659 families of existing oil tea processing enterprise, tea seed Design and Machining ability can reach 424.83 ten thousand tons, year can be processed 110.79 ten thousand tons of tea oil, working ability has 178 families in the enterprise more than 500 tons, enterprise with affinability reaches family more than 200, and oil tea processing took on a certain scale already, possessed certain basis.Oil tea byproduct comprehensive development and utilization technology is further ripe, can produce 68.39 ten thousand tons of the tea dregs of rice at present per year, can produce 70,000 tons of tea saponins.Sasanguasaponin claims theasaponin, tea saponin again, is the natural glycoside compound of a class that contains in the Theaceae oil tea fruit, and it is by seven kinds of aglucons (C30H5006), four kinds of glycosides and two kinds of a kind of pentacyclic triterpenoid saponins that organic carboxylic is formed.Tea saponin can extensively be used in fields such as food, pharmacy, daily-use chemical industry makeup, system are dyed, papermaking, printing, man-made fiber, weaving, plant pesticide.China at present can only the thick tea saponin of suitability for industrialized production, and saponin content is low, and the foreign matter content height only can only use in low-end market, and inapplicable modern science and technology is to this product volume requirement.Oil tea saponin extracts many methods, as extraction process, crystallization process, absorption method, polyamide column chromatography method, ion-exchange-resin process, flocculation agent method, ultrafiltrationmembrane process or the like, but also there are many problems in the suitability for industrialized production tea saponin: generally adopt water-containing solvents such as methyl alcohol or ethanol to extract, because organic solvent costs an arm and a leg, the production cost height, it is big that water extraction concentrates energy consumption; Membrane sepn filter membrane hole easily stop up, regenerate difficulty, production cost height.Oil tea saponin is easier to dissolving in water than in pure equal solvent, in industrial production to adopt water extraction for well, 1., how to remove impurity such as carbohydrate in the vat liquor, protein, starch, tannin, pigment effectively but also there is following subject matter in the present production of water extraction research:, in the time of water extraction leaching tea saponin, the impurity of a lot of solubilities such as carbohydrate, protein, tannin, pigment etc. also are dissolved in the water, enter filtrate with tea saponin during filtration, slag liquid separates very difficulty.2., how efficiently concentrate vat liquor, reduce production costs, with containing a large amount of moisture in the vat liquor behind the water extraction, it is big to concentrate energy consumption, time-consuming length.
Summary of the invention
Purpose of the present invention just provides and a kind ofly prepares the method for high purity sasanguasaponin from thick oil tea saponin, solves problems such as industrialization purification sasanguasaponin cost height, energy consumption are big, decon decolouring difficulty.
The present invention's technical scheme of being taked of dealing with problems is: preparing the method for high purity sasanguasaponin, can be raw material with the oil tea dregs of rice, can be raw material with thick oil tea saponin also.
When being raw material, may further comprise the steps with the oil tea dregs of rice:
1., the ultrasonic wave countercurrent extraction oil tea dregs of rice
The oil tea dregs of rice are joined in the ultrasonic wave counterflow extraction apparatus, add solvent and carry out the adverse current supersound extraction, the oil tea dregs of rice and solvent ratios are 1: 5 (weight ratio), and extraction time is 15-60 minute;
2., filter
Add 1-8ppm finings and 1-8ppm flocculating aids and clarify and filter, again with filter membrane coarse filtration, smart filter;
3., ion-exchange
Smart filtrate after the filtration is decoloured with basic anion exchange resin;
4., macroporous absorption
Adsorb with the macroporous absorption post;
5., concentrate
Organic solvent desorption liquid that contains through macroporous absorption post absorption concentrates through vacuum-evaporator, and the vacuum-evaporation thickening temperature is less than 50 ℃, drying machine with centrifugal spray drying again, through HPLC detect the Powdered sasanguasaponin of the above high purity white of content>95%.
With thick oil tea saponin is raw material, and thick oil tea saponin is that a kind of glycoside compound can be that liquid also can be powder, and its content is 50-60%.It may further comprise the steps:
1., with the thick oil tea saponin of dissolution with solvents
With thick oil tea saponin solvent, stir in the mixed precipitation jar in feed liquid 1: 20-40 (weight ratio) ratio adding belt stirrer, dissolution time normal temperature 7-10 hour, when heating for dissolving is temperature 40-50 ℃, 30-60 minute heat-up time;
2., filter
Add 1-8ppm finings and 1-8ppm flocculating aids and clarify and filter, again with filter membrane coarse filtration, smart filter;
3., ion-exchange
Smart filtrate after the filtration is decoloured with basic anion exchange resin;
4., macroporous absorption
Adsorb with the macroporous absorption post;
5., concentrate
Organic solvent desorption liquid that contains through macroporous absorption post absorption concentrates through vacuum-evaporator, and the vacuum-evaporation thickening temperature is less than 50 ℃, drying machine with centrifugal spray drying again, must through HPLC detect the Powdered sasanguasaponin of the above high purity white of content>95%.
Described solvent can be methyl alcohol, ethanol, propyl carbinol, propylene glycol, pure water.
Described finings can be higher derivative, ZTC 1+1 natural clarifying agent, carrageenin, bentonite (Bentonite), the polyvinylpolypyrrolidone (PVPP) of silicon dioxide gel (Silica sol), chitosan.
Described flocculating aids can be diatomite, silica powder, perlite, talcum powder
Described filtering membrane can be ceramic super-filtering film, organic membrane ultra-filtration membrane.
It is alkaline acrylic acid type anion exchange resin, macroreticular weakly base styrene series anion exchange resin that resin is adopted in described ion-exchange.
It is nonpolar macroporous adsorption resin basic anion exchange resin, macroporous adsorbent resin that described macroporous absorption adopts resin.
In the present invention: (1), employing ultrasonic continuous are extracted oil tea saponin in the oil tea dregs of rice; (2), adopt finings and flocculating aids macromolecular substance such as precipitate and separate carbohydrate, protein, starch, tannin, pigment for the first time; (3) adopt ceramic membrane coarse filtration, the smart small-molecule substances such as macromolecular substance such as separating carbohydrate, protein, starch, tannin, pigment for the second time and inorganic salt of filtering; (4) with the weakly basic exchange resin decolouring, macroporous adsorbent resin separates glucides such as five-carbon sugar, hexose, monose, disaccharides, polysaccharide for the third time; (5) stripping liquid concentrates in<50 ℃ of vacuum concentrators, and centrifugal spray drying gets the high purity sasanguasaponin.
The present invention's organic solvent, the thick oil tea saponin of water-containing organic solvent or water dissolution, adopt the carbohydrate in heavy clear agent and the thick oil tea saponin of the flocculating aids precipitate and separate first time, protein, starch, tannin, materials such as pigment, through the ceramic membrane coarse filtration, smart filter separates carbohydrate for the second time, protein, starch, tannin, small-molecule substances such as macromolecular substance such as pigment and inorganic salt, decolour with base exchange resin, macroporous adsorbent resin separates five-carbon sugar for the third time, hexose, monose, disaccharides, the polysaccharide glucide, stripping liquid concentrates through<50 ℃ of vacuum concentrators, and centrifugal spray drying gets>95% high purity sasanguasaponin.The present invention adopts several different methods in conjunction with small-molecule substances such as separating for several times macromolecular substance and inorganic salt; make glycoside compound obtain separating; easy obstruction and the easily saturated pressure of membrane sepn, absorption with macroporous adsorbent resin purifying have also been alleviated; obtain 95% high purity sasanguasaponin, the high purity sasanguasaponin can enter high-end fields such as food, pharmacy, electronics, printing, and this law solvent consumption is few; energy consumption is low; the extraction yield height meets national energy-saving and emission-reduction cleaner production requirement, and can carry out large-scale production.
Embodiment
The oil tea dregs of rice are joined in the ultrasonic wave counterflow extraction apparatus, adding organic solvent by the other end also can be that pure water carries out the adverse current supersound extraction, ultrasonic frequency is that 30-60KHz, ultrasonic time are 15-60 minute, ultrasonic power 12-76KW, extracting 20-60 ℃ of temperature, controlling solid-liquid ratio with liquid meter and input speed controller is 1: 5, extracting solution separates slag liquid, extracting solution feeding liquid treatment system through the slag liquid/gas separator; Adding the natural clarifying agent precipitation in setting tank goes part to remove macromolecular substance such as albumen, tannin, polysaccharide, add flocculating aids, leaching extracting solution after treatment, slough pigment with weakly basic exchange resin, must contain the oil tea saponin through two effect vacuum-evaporator evaporation recovery organic solvents and not have alcohol extract, be made into 5% aqueous solution with pure water, macroporous adsorbent resin separates glucides such as five-carbon sugar, hexose, monose, disaccharides, polysaccharide for the third time, stripping liquid concentrates in thickener, and centrifugal spray drying gets>95% high purity sasanguasaponin.
Specify below in conjunction with embodiment.
Embodiment 1
The 40-60 order oil tea dregs of rice are joined in the ultrasonic wave counterflow extraction apparatus for 1000 kilograms gradually, add 5000 kilogram of 80% (volumetric concentration) ethanol gradually by the other end and carry out the adverse current supersound extraction, ultrasonic frequency is that 30-60KHz, ultrasonic time are 15-60 minute, ultrasonic power 12-76KW, extracting 20-60 ℃ of temperature, controlling solid-liquid ratio with liquid meter and input speed controller is 1: 5, and extracting solution separates slag liquid through the slag liquid/gas separator; Extracting solution adds 60 kilograms of 5ppmZTC 1+1 natural clarifying agent precipitations and goes part to remove macromolecular substance such as albumen, tannin, polysaccharide in setting tank, add 60 kilograms of super-cells, again with filter membrane coarse filtration, smart filter; The leaching extracting solution, slough pigment with weakly basic exchange resin, must contain the oil tea saponin through two effect vacuum-evaporator evaporation recovery organic solvents and not have alcohol extract, be made into 5% aqueous solution with pure water, macroporous adsorbent resin separates glucides such as five-carbon sugar, hexose, monose, disaccharides, polysaccharide for the third time, and stripping liquid concentrates in thickener, and thickening temperature is 40-50 ℃, centrifugal spray drying gets 85.3 kilograms>95% high purity sasanguasaponin, and high purity sasanguasaponin extraction yield is 94.5%.
Embodiment 2
The 40-60 order oil tea dregs of rice 1000 are joined in the ultrasonic wave counterflow extraction apparatus gradually, add 5000 kilogram of 80% (volumetric concentration) methyl alcohol gradually by the other end and carry out the adverse current supersound extraction, ultrasonic frequency is that 30-60KHz, ultrasonic time are 15-60 minute, ultrasonic power 12-76KW, extracting 20-60 ℃ of temperature, controlling solid-liquid ratio with liquid meter and input speed controller is 1: 5, and extracting solution separates slag liquid through the slag liquid/gas separator; Extracting solution adds 60 kilograms of 5ppm ZTC 1+1 natural clarifying agent precipitations and goes part to remove macromolecular substance such as albumen, tannin, polysaccharide in setting tank, add 60 kilograms of super-cells, again with filter membrane coarse filtration, smart filter; Leaching extracting solution after treatment, slough pigment with weakly basic exchange resin, must contain the oil tea saponin through two effect vacuum-evaporator evaporation recovery organic solvents and not have alcohol extract, be made into 5% aqueous solution with pure water, macroporous adsorbent resin separates glucides such as five-carbon sugar, hexose, monose, disaccharides, polysaccharide for the third time, stripping liquid concentrates in thickener, and centrifugal spray drying gets 89.7 kilograms>95% high purity sasanguasaponin, and high purity sasanguasaponin extraction yield is 94.03%.
Embodiment 3
The 40-60 order oil tea dregs of rice 1000 are joined in the ultrasonic wave counterflow extraction apparatus gradually, add 5000 kilograms of pure water gradually by the other end and carry out the adverse current supersound extraction, ultrasonic frequency is that 30-60KHz, ultrasonic time are 15-60 minute, ultrasonic power 12-76KW, extracting 20-60 ℃ of temperature, controlling solid-liquid ratio with liquid meter and input speed controller is 1: 5, and extracting solution separates slag liquid through the slag liquid/gas separator; Extracting solution adds ZTC 1+1 natural clarifying agent precipitation and goes part to remove macromolecular substance such as albumen, tannin, polysaccharide in setting tank, add flocculating aids, again with filter membrane coarse filtration, smart filter; Leaching extracting solution after treatment, slough pigment with weakly basic exchange resin, imitate the vacuum-evaporator evaporation through two, add pure water and be made into 5% aqueous solution, macroporous adsorbent resin separates glucides such as five-carbon sugar, hexose, monose, disaccharides, polysaccharide for the third time, stripping liquid concentrates in thickener, and centrifugal spray drying gets 80.8 kilograms>91.1% high purity sasanguasaponin, and high purity sasanguasaponin extraction yield is 93.92%.
Embodiment 4
(oil tea saponin content is 50-60% to get 100 kilograms of thick oil tea saponins, weight ratio), 2000 kilogram of 80% (volume ratio) ethanol, with liquid meter and input speed controller control solid-liquid ratio is 1: 20, temperature 40-50 ℃, heating for dissolving is 1 hour in band stirring setting tank, adds 60 kilograms of 5ppmZTC 1+1 natural clarifying agents precipitations and go part to remove macromolecular substance such as albumen, tannin, polysaccharide in setting tank, add 60 kilograms of super-cells, again with filter membrane coarse filtration, smart filter; The leaching extracting solution, slough pigment with weakly basic exchange resin, must contain the oil tea saponin through two effect vacuum-evaporator evaporation recovery organic solvents and not have alcohol extract, be made into 5% aqueous solution with pure water, macroporous adsorbent resin separates glucides such as five-carbon sugar, hexose, monose, disaccharides, polysaccharide for the third time, stripping liquid concentrates in thickener, and thickening temperature is 40-50 ℃, and centrifugal spray drying gets 65 kilograms>95% high purity sasanguasaponin.

Claims (8)

1. a method for preparing the high purity sasanguasaponin is a raw material with the oil tea dregs of rice, and it may further comprise the steps:
1., ultrasonic wave countercurrent extraction
The oil tea dregs of rice are joined in the ultrasonic wave counterflow extraction apparatus, add solvent and carry out the adverse current supersound extraction, the oil tea dregs of rice and solvent ratios are 1: 5 (weight ratio), and extraction time is 15-60 minute;
2., filter
Add 1-8ppm finings and 1-8ppm flocculating aids and clarify and filter, again with filter membrane coarse filtration, smart filter;
3., ion-exchange
Smart filtrate after the filtration is decoloured with basic anion exchange resin;
4., macroporous absorption
Adsorb with the macroporous absorption post;
5., concentrate
Organic solvent desorption liquid that contains through macroporous absorption post absorption concentrates through vacuum-evaporator, and the vacuum-evaporation thickening temperature is less than 50 ℃, drying machine with centrifugal spray drying again, through HPLC detect content greater than the Powdered sasanguasaponin of 95% above high purity white.
2. a method for preparing the high purity sasanguasaponin is a raw material with thick oil tea saponin, and it may further comprise the steps:
1., with the thick oil tea saponin of dissolution with solvents
With thick oil tea saponin dissolution with solvents, stir in the mixed precipitation jar in feed liquid 1: 20-40 (weight ratio) ratio adding belt stirrer, dissolution time normal temperature 7-10 hour, when heating for dissolving is temperature 40-50 ℃, 30-60 minute heat-up time;
2., filter
Add 1-8ppm finings and 1-8ppm flocculating aids and clarify and filter, again with filter membrane coarse filtration, smart filter;
3., ion-exchange
Smart filtrate after the filtration is decoloured with basic anion exchange resin;
4., macroporous absorption
Adsorb with the macroporous absorption post;
5., concentrate
Organic solvent desorption liquid that contains through macroporous absorption post absorption concentrates through vacuum-evaporator, and the vacuum-evaporation thickening temperature is less than 50 ℃, drying machine with centrifugal spray drying again, through HPLC detect content greater than the Powdered sasanguasaponin of 95% above high purity white.
3. a kind of method for preparing the high purity sasanguasaponin according to claim 1 and 2 is characterized in that described solvent can be methyl alcohol, ethanol, propyl carbinol, propylene glycol, pure water.
4. a kind of method for preparing the high purity sasanguasaponin according to claim 1 and 2 is characterized in that described finings can be higher derivative, ZTC 1+1 natural clarifying agent, carrageenin, bentonite (Bentonite), the polyvinylpolypyrrolidone (PVPP) of silicon dioxide gel (Silica sol), chitosan.
5. a kind of method for preparing the high purity sasanguasaponin according to claim 1 and 2 is characterized in that described flocculating aids can be diatomite, silica powder, perlite, talcum powder
6. a kind of method for preparing the high purity sasanguasaponin according to claim 1 and 2 is characterized in that described filtering membrane can be ceramic super-filtering film, organic membrane, ultra-filtration membrane.
7. a kind of preparation high purity sasanguasaponin method according to claim 1 and 2 is characterized in that it is alkaline acrylic acid type anion exchange resin, macroreticular weakly base styrene series anion exchange resin that resin is adopted in described ion-exchange.
8. a kind of preparation high purity sasanguasaponin method according to claim 1 and 2 is characterized in that it is nonpolar macroporous adsorption resin basic anion exchange resin, macroporous adsorbent resin that described macroporous absorption adopts resin.
CN 201110066908 2011-03-15 2011-03-15 Method for preparing high-purity sasanquasaponins Pending CN102180935A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102372761A (en) * 2011-10-10 2012-03-14 安徽农业大学 Method for extracting tea saponin from sasanglla cake
CN102674961A (en) * 2012-05-05 2012-09-19 管天球 Organic fertilizer produced from tea cakes
CN102977162A (en) * 2012-12-17 2013-03-20 贵州泰谷农业科技有限公司 Method for producing high-purity tea saponin
CN105985400A (en) * 2015-01-29 2016-10-05 中华全国供销合作总社杭州茶叶研究所 Preparation method of active component in camellia seed
TWI571269B (en) * 2015-06-30 2017-02-21 萬能學校財團法人萬能科技大學 Extraction method of camellia oleifera abel seed, the extract, and its applications
CN111994921A (en) * 2020-08-04 2020-11-27 宁夏锦华化工有限公司 Monocyanamide decoloring method
CN112315838A (en) * 2020-11-12 2021-02-05 东莞波顿香料有限公司 Plant extract solution and preparation method and application thereof
CN113801172A (en) * 2021-09-14 2021-12-17 广州市润研基因科技有限公司 Method for separating protein in soapberry saponin water extract
WO2022268235A1 (en) * 2021-06-23 2022-12-29 广东菁萃生物科技有限公司 Saponin composition having high stability and use thereof

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CN1706863A (en) * 2005-05-12 2005-12-14 中国农业科学院油料作物研究所 Ultrasonic process of preparing theasaponin

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CN1706863A (en) * 2005-05-12 2005-12-14 中国农业科学院油料作物研究所 Ultrasonic process of preparing theasaponin

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102372761A (en) * 2011-10-10 2012-03-14 安徽农业大学 Method for extracting tea saponin from sasanglla cake
CN102674961A (en) * 2012-05-05 2012-09-19 管天球 Organic fertilizer produced from tea cakes
CN102977162A (en) * 2012-12-17 2013-03-20 贵州泰谷农业科技有限公司 Method for producing high-purity tea saponin
CN105985400A (en) * 2015-01-29 2016-10-05 中华全国供销合作总社杭州茶叶研究所 Preparation method of active component in camellia seed
TWI571269B (en) * 2015-06-30 2017-02-21 萬能學校財團法人萬能科技大學 Extraction method of camellia oleifera abel seed, the extract, and its applications
CN111994921A (en) * 2020-08-04 2020-11-27 宁夏锦华化工有限公司 Monocyanamide decoloring method
CN112315838A (en) * 2020-11-12 2021-02-05 东莞波顿香料有限公司 Plant extract solution and preparation method and application thereof
WO2022268235A1 (en) * 2021-06-23 2022-12-29 广东菁萃生物科技有限公司 Saponin composition having high stability and use thereof
CN113801172A (en) * 2021-09-14 2021-12-17 广州市润研基因科技有限公司 Method for separating protein in soapberry saponin water extract
CN113801172B (en) * 2021-09-14 2022-09-06 广州市润研基因科技有限公司 Method for separating protein in soapberry saponin water extract

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Application publication date: 20110914