CN113264976B

CN113264976B - High-purity tea saponin sodium and preparation method thereof

Info

Publication number: CN113264976B
Application number: CN202110602570.8A
Authority: CN
Inventors: 龙辉
Original assignee: Hunan Wanxiang Biotechnology Co ltd
Current assignee: Hunan Wanxiang Biotechnology Co ltd
Priority date: 2021-05-31
Filing date: 2021-05-31
Publication date: 2022-07-01
Anticipated expiration: 2041-05-31
Also published as: CN113264976A

Abstract

The invention discloses a high-purity tea saponin sodium and a preparation method thereof, and the preparation method comprises the following steps: the method comprises the following steps of crushing, sieving, soaking and deironing: crushing, sieving, soaking and removing iron from the degreased tea seed meal to obtain a mixed solution A; the method comprises the following steps of: precipitating metal ions with more than two valences in the mixed solution A by using sodium carbonate, breaking the wall by using alkaline, extracting and centrifugally separating to obtain an extracting solution; oxidizing, solubilizing and decoloring impurities: oxidizing the extracting solution, solubilizing impurities and decoloring to obtain a decoloring solution; fourthly, cooling, acid precipitation and water washing: cooling, precipitating with acid, and washing with water to obtain crude product of tea saponin acid; fifthly, dissolving, sodium treatment and impurity removal: dissolving, sodium treating and removing impurities of the crude product of tea saponin acid to obtain solution B; sixthly, concentrating and drying: concentrating and drying the solution B to obtain a high-purity tea saponin sodium product; the product has the advantages of low cost, high extraction rate of the tea saponin sodium, light product color, high purity of the tea saponin sodium, good water solubility and mechanization.

Description

High-purity tea saponin sodium and preparation method thereof

Technical Field

The invention belongs to the technical field of comprehensive utilization of oil meal, and particularly relates to high-purity tea saponin sodium and a preparation method thereof.

Background

Tea saponin, which is a typical glycoside substance, is a mixture of various glycoside components. The tea saponin is composed of three parts of organic acid, aglycone and saccharide, wherein the organic acid in the structure is angelic acid, acetic acid and tiglic acid; the aglycone is beta-amyrin (beta-amyrin) derivative, and the basic carbon frame is oleanane; the organic acid is connected with the hydroxyl on the C-21 or C-22 position on the E ring in the aglycone through ester bond to form composite aglycone; the glycosyl part consists of arabinose, galactose, xylose and glucuronic acid, four monosaccharides are linked through glycosidic bonds to form tetrasaccharides, and hydroxyl on glucuronic acid C-1 in the tetrasaccharides and hydroxyl on complex aglycone C-1 are linked through glycosidic bonds generated by dehydration to form tea saponin. The tea saponin has acidity due to the carboxyl (-COOH) of glucuronic acid in the molecular structure, and can be called tea saponin acid, and the structure of the tea saponin is shown in the following formula.

The connection of different aglycones and different organic acids and the different connection modes lead to a series of tea saponin monomers with similar structures and a plurality of varieties. The Japanese scholars Qingshan Xinxianlang is separated from tea tree seeds for the first time to obtain tea saponin, and aglycone and saccharide are obtained through a hydrolysis experiment so as to determine the chemical formula of the tea saponin. In 1952, the crystal of tea saponin was first separated from tea seeds by Shishimen and Shangyang of university of Tokyo, Japan, and the melting point was determined to be 224-₅₇H₉₀O₂₆。

The pure product of tea saponin is milk white or light yellow powder, has strong hygroscopicity, and the aqueous solution of the tea saponin is acidic to methyl red reaction (tea saponin acid). The acidic tea saponin is insoluble in cold water, absolute ethyl alcohol and absolute methyl alcohol, insoluble in organic solvents such as ethyl ether, acetone, benzene, petroleum ether and the like, slightly soluble in warm water, ethyl acetate and carbon disulfide, and well soluble in hot water, alkaline water solution, aqueous ethyl alcohol, aqueous methyl alcohol, n-butyl alcohol, glacial acetic acid, pyridine and dried vinegar, and can be extracted by the media. Under the condition that the pH value is more than pK (the dissociation constant of carboxyl of glucuronic acid in the tea saponin), the tea saponin acid can be converted into tea saponin acid salt, tea saponin sodium and tea saponin potassium, the solubility of the tea saponin acid salt, the tea saponin acid salt and the tea saponin potassium in water is higher, and the tea saponin in the tea seed meal can be extracted by utilizing the principle; the salt of tea saponin acid with divalent metal ion and trivalent metal ion, such as calcium tea saponin, magnesium tea saponin, ferrous tea saponin and ferric tea saponin, is the precipitate of water insoluble white cloud. Therefore, the chelation and precipitation of the inherent and foreign polluted divalent metal ions and trivalent metal ions in the tea seed meal are beneficial to improving the yield of the tea saponin. Through repeated data analysis and experimental comparison, the applicant finds that most researchers confuse the fundamental differences of tea saponin, tea saponin acid and tea saponin acid salt.

Because the molecular structure has hydrophilic saccharide and hydrophobic aglycone, the tea saponin has good surface activity and is a natural surfactant. According to research, the HLB value of the tea saponin is 9.2, and the tea saponin is suitable for forming oil-in-water type emulsion. Therefore, the tea saponin can be used as a raw material of high-grade washing liquid for producing fruit and vegetable cleaning agents, shampoos, shower gels, hand washing liquids and foot washing liquids. The tea saponin has inhibitory effect on various microorganisms. According to the research, the tea saponin has obvious inhibiting effect on escherichia coli, bacillus subtilis, staphylococcus aureus and saccharomycetes, has certain inhibiting effect on candida albicans, can partially inhibit the propagation of some moulds causing food deterioration, has gram-positive bacteria and gram-negative bacteria in the inhibited bacteria, has both cocci and bacilli, and has broad-spectrum inhibiting effect on tea saponin, so the tea saponin has the application prospect of a preservative. The tea saponin also has the action of like biological hormone, and has promoting effect on growth of animals and plants. In addition, the tea saponin also has physiological activities of inhibiting alcohol absorption, protecting gastrointestinal tract, resisting hypertension, resisting permeability and diminishing inflammation, etc. Therefore, the market demands a high-purity tea saponin product.

Because the yield of tea seeds is small, the production of tea oil mainly adopts a squeezing process. At present, tea seed meal (also called tea seed cake and tea seed cake) obtained after tea seed is squeezed to extract tea seed oil and degreased tea seed meal obtained after residual oil is extracted from the tea seed meal by a leaching method are basically in a waste state, so that environmental pollution and resource waste are caused. Through repeated and careful experimental study, the applicant discovers that the tea seed meal contains iron filings for the first time, and the analysis reason is that the iron filings exist, which not only affect the color of the tea saponin product, but also are not beneficial to the full extraction of the tea saponin because the screw roller of the screw press slightly falls off due to the repeated friction and extrusion of high pressure in the process of squeezing and extracting oil by the screw press after shelling. The tea seed meal, the defatted tea seed meal, the tea seed hulls and the tea seed cattails contain 5-20% of tea saponin and other useful components such as protein, polysaccharide, flavone and the like, so that how to synthesize the tea seed meal, the defatted tea seed meal, the tea seed hulls and the tea seed cattails is necessary, urgent and important.

Chinese patents CN201910463338.3 (a method for extracting and refining tea saponin), CN201911119365.5 (a method for extracting tea saponin from camellia oleifera fruit shell), CN201910615565.3 (a method for extracting tea saponin), CN202010475217.3 (a process for extracting tea saponin from camellia oleifera seed cake and its application in amino acid facial soap), CN201710839054.0 (a method for improving the dissolution rate of water-extracted tea saponin), CN201811402817.6 (a method for extracting tea saponin from camellia oleifera seeds), CN201611008220.4 (a method for simultaneously recovering ethanol and tea saponin from the aqueous phase after extracting camellia oleifera seed oil by ethanol water extraction), CN201810246415.5 (a separation method for improving the yield of tea saponin), CN201910046926.7 (a method for extracting tea saponin), CN201910463338.3 (a method for extracting and refining tea saponin), CN201810864405.8 (a method for preparing tea saponin), CN201910615565.3 (a method for extracting tea saponin), CN201910802169.1 (a method for refining high-purity tea saponin), CN201911196405.6 (a method for extracting tea saponin from camellia oleifera seed oil and tea saponin) and CN201711296589.4 (a method for efficiently decontaminating natural high-purity tea saponin Preparation method of tea saponin), which respectively relates to the processes and technologies of extraction, preparation, purification and refining of tea saponin, however, the patents have the following defects: 1. the properties of the tea saponin are not well known, so the technical scheme adopted has the defects of being congenital or the like; 2. the developed tea saponin product has low extraction rate or low purity, so that the technology is not advanced and the economy is unreasonable. Therefore, continuous research on the extraction and refining technology of the tea saponin and development of new technology and new process with high extraction rate and high purity of the tea saponin have important social, economic and practical significance.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide the high-purity tea saponin sodium, which has the advantages of high extraction rate, low cost, high purity of the tea saponin sodium, full utilization of raw materials, light product color, good water solubility and mechanized manufacture.

In addition, the invention also aims to provide a preparation method of the high-purity tea saponin sodium, which is easy to implement and has the advantages of convenient operation, outstanding product characteristics, easy equipment type selection and matching, low equipment investment, high additional value of products, good economic benefit, mechanization and the like.

In order to achieve the purpose, the invention is realized by the following scheme:

a preparation method of high-purity tea saponin sodium comprises the following steps:

(1) crushing, sieving, soaking and removing iron: firstly, crushing defatted tea seed meal by using a stainless steel crusher and sieving the crushed defatted tea seed meal by using a standard sieve of 40-100 meshes to obtain defatted tea seed meal; adding the obtained degreased tea seed meal into softened water, stirring and soaking at room temperature, removing scrap iron in the mixture by using an iron remover after stirring and soaking are finished, and obtaining degreased tea seed meal soaking mixed liquor after scrap iron removal for later use;

(2) alkaline wall breaking and extraction:

A. adding sodium carbonate into the prepared degreasing tea seed meal soaking mixed liquid without the iron filings, stirring for 0.5-2.0 hours at the temperature of 60-80 ℃, and obtaining mixed liquid A after stirring for later use;

B. under the condition of stirring, adjusting the pH value of the mixed solution A to 11.1-11.5 by using a sodium hydroxide solution, stirring for 0.5-2.0 hours at the temperature of 60-80 ℃, and after stirring, performing centrifugal separation to obtain an extracting solution a1 and tea seed meal b1 for later use;

C. adding softened water into the tea seed meal residue B1 obtained in the step B, carrying out secondary extraction according to the method for the primary extraction in the step B, and removing the precipitate to obtain an extracting solution a 2; mixing the extract a1 and the extract a2 to obtain an extract mixed solution for later use;

(3) oxidation, impurity solubilization and decolorization: under the condition of stirring, adding a traceless oxidant into the extract mixed solution obtained in the step II, and continuously stirring for 5-45 hours to obtain an oxidation solubilization decolorant for later use;

(4) cooling, acid precipitation and water washing: under the condition of stirring, firstly reducing the temperature of the oxidation solubilization decolorization solution obtained in the step three to 0-20 ℃, then adjusting the pH of the oxidation solubilization decolorization solution to 3.1-3.3 by using a hydrochloric acid solution, continuously stirring for 0.5-1.5 hours, performing centrifugal separation after stirring, and removing supernatant to obtain an acidified tea saponin acid precipitate crude product; adding softened water with the temperature of 0-20 ℃ and the pH of 3.1-3.3 into the acidified tea saponin acid precipitation crude product, stirring for 1.0-2.0 hours for first washing, performing centrifugal separation after stirring, and removing supernatant to obtain the acidified tea saponin acid precipitation crude product after the first washing; and (4) carrying out secondary washing according to the method of the primary washing to obtain the acidified tea saponin acid precipitate crude product after water washing for later use.

(5) Dissolution, sodium treatment and impurity removal: adding an ethanol water solution into the water-washed acidified tea saponin acid precipitation crude product obtained in the step four, heating the mixed solution to 30-50 ℃ under the condition of cooling and refluxing, stirring for 0.5-2.5 hours, performing centrifugal separation after stirring, and removing the precipitate to obtain an acidified ethanol-water solution of tea saponin acid; under the condition of stirring, adjusting the pH value of the acidified ethanol-water solution of the tea saponin acid to 5.5-6.5 by using a sodium hydroxide solution, continuously stirring for 0.5-3.5 hours, performing centrifugal separation after stirring is finished, and removing the precipitate to obtain the ethanol-water solution of the tea saponin sodium for later use.

(6) Concentration and drying: concentrating and recovering ethanol in the ethanol-water solution of the sodium tea saponin prepared by the step fifthly by using a vacuum concentration method to obtain concentrated solution of the sodium tea saponin; and drying the obtained concentrated solution of the sodium theasapogeninate until the percentage content of water is less than or equal to 5 percent, thus obtaining the white-to-light yellow high-purity sodium theasapogeninate product.

Preferably, the degreased tea seed meal in the step is pressed tea seed meal obtained after tea seed oil is extracted from tea seeds by pressing through a pressing method, and the tea seed meal with the oil content of less than or equal to 1.0% is obtained after residual oil in the pressed tea seed meal is removed through a leaching method; the iron remover is used in food industry or chemical industry; the mass ratio of the degreased tea seed meal to the softened water is 1:6-10, and the stirring and soaking time is 2-20 hours.

Preferably, the sodium carbonate is industrial-grade, chemically pure or analytically pure sodium carbonate; the sodium hydroxide is industrial grade, chemically pure or analytically pure sodium hydroxide;

preferably, the mass ratio of the mixed solution of the degreased tea seed meal soaked with the iron filings in the step A to the sodium carbonate is 100:0.05-1, and the mass ratio of the tea seed meal b1 to the softened water in the step C is 1: 1.5-4.5.

Preferably, the traceless oxidant in the step three is industrial, chemically pure or analytically pure hydrogen peroxide or ozone water prepared by an ozone generator; the mass ratio of the extracting solution mixed solution to the traceless oxidant is 100: 0.001-0.5.

Preferably, the hydrochloric acid in the fourth step is industrial-grade, chemically pure or analytically pure hydrochloric acid; the mass ratio of the acidified crude tea saponin acid precipitate product to the softened water is 1:1.5-3.5

Preferably, the volume percentage of the ethanol in the ethanol aqueous solution in the step (5) is 75-80%, and the mass ratio of the acidified tea saponin acid precipitation crude product after water washing to the ethanol aqueous solution is 1: 2.5-5.5.

Preferably, the ethanol in the step fifthly is industrial-grade, chemically pure or analytically pure ethanol; the sodium hydroxide is industrial grade, chemically pure or analytically pure sodium hydroxide.

Preferably, the step sixteenth is dried under normal pressure, vacuum or spray.

In addition, the invention also discloses the high-purity tea saponin sodium prepared by any one of the preparation methods.

The technical concept of the invention is as follows:

the invention utilizes the properties that iron filings in the degreased tea seed meal after soaking, softening and expansion can be separated by an iron remover, divalent and polyvalent metal ions in the degreased tea seed meal and sodium carbonate generate water-insoluble carbonate precipitates to be removed, water-insoluble tea saponin acid salt combined with the divalent and polyvalent metal ions can be converted into water-soluble tea saponin sodium, pectin and protein forming plant cell walls can be dissolved in an alkaline solution to be wall-broken, tea saponin acid originally existing in the cell walls and after wall breaking can be soluble in water under the heating alkaline condition, colored organic substances can be oxidized, decolored and hydroxylated to be solubilized, the tea saponin acid can not be dissolved in water under the low temperature and acidic condition and water-soluble impurities can be dissolved in water, the tea saponin acid can be dissolved in a higher-concentration ethanol water solution but macromolecular impurities can not be dissolved, the tea saponin acid can be neutralized and sodified to generate the tea saponin sodium and can be dissolved in the higher-concentration ethanol water solution but the macromolecular impurities can not be dissolved, crushing and sieving defatted tea seed meal, soaking and removing iron to obtain a soaking mixture, and performing alkaline wall breaking, extraction and centrifugal separation to obtain an extracting solution of the mixture; performing oxidation, impurity solubilization and decolorization on the extract of the mixture to obtain an oxidation solubilization decolorization solution, and performing cooling, acid precipitation, centrifugal separation, water washing and centrifugal separation on the oxidation solubilization decolorization solution to obtain an acidified crude tea saponin acid precipitate; dissolving the crude product of the tea saponin acid precipitate with a higher-concentration ethanol water solution, performing centrifugal separation, sodium treatment and centrifugal separation to remove insoluble macromolecular impurities to obtain an ethanol-water solution of the tea saponin sodium, performing vacuum concentration and ethanol recovery to obtain a concentrated solution of the tea saponin sodium, and performing drying dehydration to obtain the high-purity tea saponin sodium.

Compared with the prior art, the invention has the beneficial effects that:

(1) the method of the invention uses a stainless steel crusher to crush degreased tea seed meal, soak and fully expand, and disperses the degreased tea seed meal, and then uses an iron remover to remove scrap iron brought into the tea seed meal by oil extraction through pressing of a screw press, solves the technical problems and difficulties that iron rust brought into the tea seed meal crushed by a common crusher changes color under the action of the iron rust and polyphenols inherent in the tea seed meal, iron rust reacts with tea saponin to generate water-insoluble iron tea saponin to reduce the extraction rate of the tea saponin, iron filings brought into the tea seed meal by the squeezing and oil extraction of a screw squeezer cannot be removed usually, the iron filings change color under the action of the iron filings and polyphenols, the iron filings react with the tea saponin to generate water-insoluble iron tea saponin to reduce the extraction rate of the tea saponin in the subsequent extraction process, and the like, the technical effects of reducing subsequent oxidation decoloration load and difficulty, improving subsequent color and purity of the tea saponin sodium product and improving subsequent yield of the tea saponin sodium product are mainly achieved.

(2) The method fully generates insoluble carbonate precipitate by using sodium carbonate to react with divalent and polyvalent metal ions inherent in degreased tea seed meal so as to fully dissociate the tea saponin combined with the divalent and polyvalent metal ions and simultaneously convert the insoluble combined tea saponin into water-soluble tea saponin sodium; the method comprises the following steps of heating under an alkaline condition (pH is 11.1-11.5), fully dissolving protein and pectin forming cell walls to disintegrate the cell walls, fully releasing, dissolving and extracting the sodium tea saponin existing in the cell walls, solving the technical problems that the extraction rate of the sodium tea saponin is low due to the fact that the inherent divalent and polyvalent metal ions of tea seed cakes are combined with the tea saponin to form insoluble tea saponin acid salt, solving the technical problems and difficulties that the sodium tea saponin originally existing in the cell walls is difficult to dissolve out and extract due to the fact that the thick plant cell walls are not damaged and disintegrated, the extraction rate is low and the like, and mainly achieving the technical effects of fully extracting the sodium tea saponin and remarkably improving the extraction rate of the sodium tea saponin.

(3) The method of the invention uses traceless oxidant to fully oxidize and fade the pigment in the extracting solution of the mixture, fully oxidize and hydroxylate the flavone, alkaloid and other components with lower polarity in the extracting solution of the mixture into substances with increased polarity and water solubility to solubilize, thereby solving the technical problems that the decolorant impurity is difficult to be brought in and the decolorant of the sodium theasaponin solution with dark color is difficult to be brought in, the separation of the original flavone, alkaloid and other components with lower polarity and tea saponin acid with lower polarity is difficult to be realized, and the technical effects of fully decoloring, improving the whiteness of the product, improving the separation effect of the substances with similar polarity, improving the purity of the subsequent product and bringing no decolorant impurity are mainly achieved.

(4) The method of the invention uses the technical treatment of converting the sodium tea saponin into the tea saponin acid by using low temperature (0-20 ℃) and soft pH (3.1-3.3) and removing water-soluble impurities by washing with water at low temperature and soft pH, solves the technical problems and difficulties that the solubility of the tea saponin acid is higher and the yield of the tea saponin acid is lower due to overhigh temperature and too low pH (namely too strong acidity such as 1-3) of the acidified precipitated tea saponin acid, changes the inherent structure of the tea saponin acid and lowers the yield due to the hydrolysis of glycosidic bonds in the tea saponin acid caused by higher temperature and too low pH (namely too strong acidity), the method mainly achieves the technical effects of reducing the solubility of the acidified tea saponin acid, fully precipitating the acidified tea saponin acid, fully removing water-soluble impurities, keeping the inherent molecular structure of the tea saponin acid and improving the yield and the purity of the acidified tea saponin acid.

(5) The method solves the technical problems and difficulties that the tea saponin acid and the tea saponin sodium are difficult to separate from macromolecular impurities, so that the product purity is low, the ethanol consumption is large, the cost is high and the like, and mainly achieves the technical effects of reducing the ethanol consumption, fully separating the macromolecular impurities, reducing the cost and improving the product purity.

Compared with the prior art, the invention has the advantages that the tea saponin product with low purity, deep color, high cost and low extraction rate can be obtained by only using the tea seed meal or the degreased tea seed meal as the raw material and processing the raw material by respective technologies in the prior art; the invention realizes the technical breakthrough of preparing the sodium theasapogenin product with high purity, light color, low cost and high extraction rate by using the degreased tea seed meal as the raw material.

Drawings

Fig. 1 is a process flow chart of the preparation method of high-purity sodium theasapogenin according to the invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

(1) crushing, sieving, soaking and removing iron: firstly, crushing defatted tea seed meal by using a stainless steel crusher and sieving the crushed defatted tea seed meal by using a 70-mesh standard sieve to obtain defatted tea seed meal powder; then adding 50kg of the obtained degreased tea seed meal into 400kg of softened water, stirring for 11 hours at room temperature, removing scrap iron in the mixture by using an iron remover after stirring is finished, and obtaining degreased tea seed meal soaking mixed liquor after scrap iron removal for later use;

(2) alkaline wall breaking and extraction:

A. adding sodium carbonate with the mass of 0.525% into the prepared degreasing tea seed meal soaking mixed liquid without the iron filings, stirring for 1.25 hours at 70 ℃, and obtaining mixed liquid A after stirring for later use;

B. under the condition of stirring, adjusting the pH value of the mixed solution A to 11.3 by using a sodium hydroxide solution, stirring for 1.25 hours at 70 ℃, and performing centrifugal separation after stirring to obtain an extracting solution a1 and tea seed meal residue b1 for later use;

C. adding softened water with the mass being 3 times of that of the tea seed meal residue B1 obtained in the step B, carrying out secondary extraction according to the method for primary extraction in the step B, and removing the precipitate to obtain an extracting solution a 2; mixing the extract a1 and the extract a2 to obtain an extract mixed solution for later use;

(3) oxidation, impurity solubilization and decolorization: under the condition of stirring, adding hydrogen peroxide with the mass of 0.25% into the extract mixed liquor obtained in the step II, and continuously stirring for 25 hours to obtain oxidation solubilization decolorant for later use;

(4) cooling, acid precipitation and water washing: under the condition of stirring, firstly reducing the temperature of the oxidation solubilization decolorization solution obtained in the step three to 10 ℃, then regulating the pH of the oxidation solubilization decolorization solution to 3.2 by using a hydrochloric acid solution, continuing stirring for 1 hour, performing centrifugal separation after the stirring is finished, and removing supernatant to obtain an acidified tea saponin acid precipitation crude product; adding softened water with the mass 2.5 times of the weight of the crude acid precipitation product of the tea saponin, the temperature of which is 10 ℃ and the pH value of which is 3.2 into the crude acid precipitation product of the tea saponin, stirring for 1.5 hours to carry out primary washing, carrying out centrifugal separation after the washing is finished, and removing supernate to obtain the crude acid precipitation product of the tea saponin after the primary washing; and (4) carrying out secondary washing according to the method of the primary washing to obtain the acidified tea saponin acid precipitate crude product after water washing for later use.

(5) Dissolving, sodium treatment and impurity removal: adding an ethanol water solution with the ethanol volume percentage of 77.5 percent and the mass 4 times that of the acidified tea saponin acid precipitation crude product obtained in the step four into the acidified tea saponin acid precipitation crude product obtained in the step four, heating the mixed solution to 40 ℃ under the condition of cooling reflux, stirring for 1.5 hours, performing centrifugal separation after stirring, and removing the precipitation to obtain an acidified ethanol-water solution of tea saponin acid; under the condition of stirring, adjusting the pH value of the acidified ethanol-water solution of the tea saponin acid to 6 by using a sodium hydroxide solution, continuously stirring for 2 hours, carrying out centrifugal separation after stirring is finished, and removing the precipitate to obtain the ethanol-water solution of the tea saponin sodium for later use.

(6) Concentration and drying: concentrating and recovering ethanol in the ethanol-water solution of the sodium tea saponin prepared by the step fifthly by using a vacuum concentration method to obtain concentrated solution of the sodium tea saponin; drying the obtained concentrated solution of the sodium theasapogeninate until the percentage content of water is less than or equal to 5 percent, thus obtaining 6.25 kg of a light yellow high-purity sodium theasapogeninate product.

The obtained high-purity tea saponin sodium product is light yellow powder, and the yield is 6.25/50-12.5%. Determining that the purity of the tea saponin of the obtained tea saponin sodium product is 96.8% by adopting an acid hydrolysis-acetone Soxhlet extraction-constant weight method in the chemical industry standard HG/T4492-2013 natural nonionic surfactant tea saponin, multiplying the purity by a conversion coefficient of 1.018(1245.54/1223.54) to convert the tea saponin into the tea saponin sodium, wherein the purity of the tea saponin sodium of the obtained tea saponin sodium product is 98.5%; the pH value of a high-purity tea saponin sodium product (1% water solution) is 5.9-6.1 by adopting a pH measuring method in the chemical industry standard HG/T4492-2013 natural non-ionic surfactant tea saponin of the people's republic of China.

Example 2

(1) crushing, sieving, soaking and removing iron: firstly, crushing defatted tea seed meal by using a stainless steel crusher and sieving the crushed defatted tea seed meal by using a 100-mesh standard sieve to obtain defatted tea seed meal powder; then adding 100kg of the obtained degreased tea seed meal into 1000kg of softened water, stirring for 20 hours at room temperature, removing scrap iron in the mixture by using an iron remover after stirring is finished, and obtaining degreased tea seed meal soaking mixed liquor after scrap iron removal for later use;

(2) alkaline wall breaking and extraction:

A. adding 1% by mass of sodium carbonate into the degreased tea seed meal soaking mixed liquor which is prepared in the step I and is subjected to scrap iron removal, stirring for 2 hours at 80 ℃, and obtaining mixed liquor A after stirring for later use;

B. under the condition of stirring, adjusting the pH value of the mixed solution A to 11.5 by using a sodium hydroxide solution, stirring for 2 hours at the temperature of 80 ℃, and after stirring, performing centrifugal separation to obtain an extracting solution a1 and tea seed meal residue b1 for later use;

C. adding softened water with the mass being 4.5 times of that of the tea seed meal residue B1 obtained in the step B, carrying out secondary extraction according to the method for primary extraction in the step B, and removing the precipitate to obtain an extracting solution a 2; mixing the extract a1 and the extract a2 to obtain an extract mixed solution for later use;

(3) oxidation, impurity solubilization and decolorization: under the condition of stirring, adding hydrogen peroxide with the mass of 0.5% into the extract mixed liquor obtained in the step II, and continuously stirring for 45 hours to obtain oxidation solubilization decolorant for later use;

(4) cooling, acid precipitation and water washing: under the condition of stirring, firstly reducing the temperature of the oxidation solubilization decolorization solution obtained in the step three to 0 ℃, then regulating the pH of the oxidation solubilization decolorization solution to 3.1 by using a hydrochloric acid solution, continuing stirring for 1.5 hours, performing centrifugal separation after the stirring is finished, and removing a supernatant to obtain an acidified crude product of the tea saponin acid precipitate; adding softened water with the mass of 3.5 times of that of the acid precipitated crude product of the tea saponin, the temperature of which is 0 ℃ and the pH value of which is 3.1 into the acid precipitated crude product of the tea saponin, stirring for 2 hours to carry out primary washing, carrying out centrifugal separation after the washing is finished, and removing supernatant to obtain the acid precipitated crude product of the tea saponin after the primary washing; and (4) carrying out secondary washing according to the method of the primary washing to obtain the acidified tea saponin acid precipitate crude product after water washing for later use.

(5) Dissolving, sodium treatment and impurity removal: adding an ethanol water solution with the mass of 80% and 5.5 times of that of the water-washed acidified tea saponin acid precipitation crude product into the water-washed acidified tea saponin acid precipitation crude product, heating the mixed solution to 50 ℃ under the condition of cooling and refluxing, stirring for 2.5 hours, performing centrifugal separation after stirring, and discarding the precipitation to obtain an acidified ethanol-water solution of tea saponin acid; under the condition of stirring, adjusting the pH value of the acidified ethanol-water solution of the tea saponin acid to 6.5 by using a sodium hydroxide solution, continuously stirring for 3.5 hours, performing centrifugal separation after stirring is finished, and removing the precipitate to obtain the ethanol-water solution of the tea saponin sodium for later use.

(6) Concentration and drying: concentrating and recovering ethanol in the ethanol-water solution of the sodium tea saponin prepared by the step fifthly by using a vacuum concentration method to obtain concentrated solution of the sodium tea saponin; drying the obtained concentrated solution of the sodium theasapogeninate until the percentage content of water is less than or equal to 5 percent, thus obtaining 15kg of white high-purity sodium theasapogeninate product.

The obtained high-purity tea saponin sodium product is light yellow powder, and the yield is 15/100-15.0%. Determining that the purity of the tea saponin of the obtained tea saponin sodium product is 97.8% by adopting an acid hydrolysis-acetone Soxhlet extraction-constant weight method in the chemical industry standard HG/T4492-2013 natural nonionic surfactant tea saponin, multiplying the purity by a conversion coefficient 1.018(1245.54/1223.54) to convert the tea saponin into the tea saponin sodium, wherein the purity of the tea saponin sodium of the obtained tea saponin sodium product is 99.5%; the pH value of a high-purity tea saponin sodium product (1% water solution) is 6.4-6.6 by adopting a pH measuring method in the chemical industry standard HG/T4492-2013 natural non-ionic surfactant tea saponin of the people's republic of China.

Example 3

(1) crushing, sieving, soaking and removing iron: firstly, crushing defatted tea seed meal by using a stainless steel crusher and sieving the crushed defatted tea seed meal by using a 40-mesh standard sieve to obtain defatted tea seed meal powder; then adding 300kg of the obtained degreased tea seed meal into 1800kg of softened water, stirring for 2 hours at room temperature, removing scrap iron in the mixture by using an iron remover after stirring is finished, and obtaining degreased tea seed meal soaking mixed liquor after scrap iron removal for later use;

(2) alkaline wall breaking and extraction:

A. adding sodium carbonate with the mass of 0.05% into the prepared degreasing tea seed meal soaking mixed liquor without the iron filings, stirring for 0.5 hour at 60 ℃, and obtaining mixed liquor A after stirring for later use;

B. under the condition of stirring, adjusting the pH value of the mixed solution A to 11.1 by using a sodium hydroxide solution, stirring for 0.5 hour at 60 ℃, and performing centrifugal separation after stirring to obtain an extracting solution a1 and tea seed meal residue b1 for later use;

C. adding softened water with the mass being 1.5 times of that of the tea seed dregs B1 obtained in the step B, carrying out secondary extraction according to the method for the primary extraction in the step B, and removing the precipitate to obtain an extracting solution a 2; mixing the extract a1 and the extract a2 to obtain an extract mixed solution for later use;

(3) oxidation, impurity solubilization and decolorization: under the condition of stirring, adding 0.001 mass percent of ozone into the extract mixed solution obtained in the step II, and continuously stirring for 5 hours to obtain oxidation solubilization decolorant for later use;

(4) cooling, acid precipitation and water washing: under the condition of stirring, firstly reducing the temperature of the oxidation solubilization decolorization solution obtained in the step three to 20 ℃, then regulating the pH of the oxidation solubilization decolorization solution to 3.3 by using a hydrochloric acid solution, continuing stirring for 0.5 hour, performing centrifugal separation after the stirring is finished, and removing the supernatant to obtain an acidified tea saponin acid precipitate crude product; adding softened water with the temperature of 20 ℃ and the pH value of 3.3, the mass of which is 3.3 times that of the acidified tea saponin acid precipitation crude product, stirring for 1 hour for carrying out primary washing, carrying out centrifugal separation after the washing is finished, and removing supernatant to obtain the acidified tea saponin acid precipitation crude product after the primary washing; and (4) carrying out secondary washing according to the method of the primary washing to obtain the acidified tea saponin acid precipitate crude product after water washing for later use.

(5) Dissolving, sodium treatment and impurity removal: adding an ethanol water solution with the mass of 75% and 2.5 times of that of the water-washed acidified tea saponin acid precipitation crude product into the water-washed acidified tea saponin acid precipitation crude product, heating the mixed solution to 30 ℃ under the condition of cooling and refluxing, stirring for 0.5 hour, performing centrifugal separation after stirring, and discarding the precipitation to obtain an acidified ethanol-water solution of tea saponin acid; under the condition of stirring, adjusting the pH value of the acidified ethanol-water solution of the tea saponin acid to 5.5 by using a sodium hydroxide solution, continuously stirring for 0.5 hour, performing centrifugal separation after stirring is finished, and removing the precipitate to obtain the ethanol-water solution of the tea saponin sodium for later use.

(6) Concentration and drying: concentrating and recovering ethanol in the ethanol-water solution of the sodium tea saponin prepared by the step fifthly by using a vacuum concentration method to obtain concentrated solution of the sodium tea saponin; drying the obtained concentrated solution of the tea saponin sodium until the water content is less than or equal to 5 percent, thus obtaining 30 kg of light yellow high-purity tea saponin sodium product.

The obtained high-purity tea saponin sodium product is light yellow powder, and the yield is 30/300-10.0%. Determining that the purity of the tea saponin of the obtained tea saponin sodium product is 96.4% by adopting an acid hydrolysis-acetone Soxhlet extraction-constant weight method in the chemical industry standard HG/T4492-2013 natural nonionic surfactant tea saponin, multiplying the purity by a conversion coefficient 1.018(1245.54/1223.54) to convert the tea saponin into the tea saponin sodium, wherein the purity of the tea saponin sodium of the obtained tea saponin sodium product is 98.1%; the pH of a high-purity tea saponin sodium product (1% aqueous solution) is 5.4-5.6 by adopting a pH measuring method in chemical industry standard HG/T4492-2013 natural non-ionic surfactant tea saponin of the people's republic of China.

Example 4

(1) crushing, sieving, soaking and removing iron: firstly, crushing defatted tea seed meal by using a stainless steel crusher and sieving the crushed defatted tea seed meal by using a 80-mesh standard sieve to obtain defatted tea seed meal powder; then adding 500kg of the obtained degreased tea seed meal into 4500kg of softened water, stirring for 15 hours at room temperature, and removing iron filings in the mixture by using an iron remover after stirring to obtain degreased tea seed meal soaking mixed liquor after removing the iron filings for later use;

(2) alkaline wall breaking and extraction:

A. adding sodium carbonate with the mass of 0.8% into the prepared degreasing tea seed meal soaking mixed liquor without the iron filings, stirring for 1.5 hours at 75 ℃, and obtaining mixed liquor A after stirring for later use;

B. under the condition of stirring, adjusting the pH value of the mixed solution A to 11.4 by using a sodium hydroxide solution, stirring for 1.5 hours at 75 ℃, and performing centrifugal separation after stirring to obtain an extracting solution a1 and tea seed meal residue b1 for later use;

C. adding softened water with the mass being 4 times of that of the tea seed meal residue B1 obtained in the step B, carrying out secondary extraction according to the method for primary extraction in the step B, and removing the precipitate to obtain an extracting solution a 2; mixing the extract a1 and the extract a2 to obtain an extract mixed solution for later use;

(3) oxidation, impurity solubilization and decolorization: under the condition of stirring, adding hydrogen peroxide with the mass of 0.4% into the extract mixed liquor obtained in the step II, and continuously stirring for 40 hours to obtain oxidation solubilization decolorant for later use;

(4) cooling, acid precipitation and water washing: under the condition of stirring, firstly reducing the temperature of the oxidation solubilization decolorization solution obtained in the step three to 5 ℃, then regulating the pH of the oxidation solubilization decolorization solution to 3.1 by using a hydrochloric acid solution, continuing stirring for 1.8 hours, carrying out centrifugal separation after the stirring is finished, and removing the supernatant to obtain an acidified tea saponin acid precipitate crude product; adding softened water with the temperature of 5 ℃ and the pH value of 3.1, the mass of which is 3 times that of the acidified tea saponin acid precipitation crude product, stirring for 1.8 hours to carry out primary washing, carrying out centrifugal separation after the washing is finished, and discarding supernatant to obtain the acidified tea saponin acid precipitation crude product after the primary washing; and (4) carrying out secondary washing according to the method of the primary washing to obtain the acidified tea saponin acid precipitate crude product after water washing for later use.

(5) Dissolving, sodium treatment and impurity removal: adding an ethanol water solution with the mass of 80% and 5 times of that of the acidified tea saponin acid precipitation crude product obtained in the step four, heating the mixed solution to 45 ℃ under the condition of cooling and refluxing, stirring for 2 hours, performing centrifugal separation after stirring, and removing the precipitate to obtain an acidified ethanol-water solution of tea saponin acid; under the condition of stirring, adjusting the pH value of the acidified ethanol-water solution of the tea saponin acid to 6.3 by using a sodium hydroxide solution, continuously stirring for 3 hours, performing centrifugal separation after stirring is finished, and removing the precipitate to obtain the ethanol-water solution of the tea saponin sodium for later use.

(6) Concentration and drying: concentrating and recovering ethanol in the ethanol-water solution of the sodium tea saponin prepared by the step fifthly by using a vacuum concentration method to obtain concentrated solution of the sodium tea saponin; and drying the obtained concentrated solution of the sodium theasapogeninate until the percentage content of water is less than or equal to 5 percent, thereby obtaining 70 kilograms of white high-purity sodium theasapogeninate products.

The obtained high-purity tea saponin sodium product is light yellow powder, and the yield is 70/500-14.0%. Determining that the purity of the tea saponin of the obtained tea saponin sodium product is 97.3% by adopting an acid hydrolysis-acetone Soxhlet extraction-constant weight method in the chemical industry standard HG/T4492-2013 natural nonionic surfactant tea saponin, multiplying the purity by a conversion coefficient 1.018(1245.54/1223.54) to convert the tea saponin into the tea saponin sodium, wherein the purity of the tea saponin sodium of the obtained tea saponin sodium product is 99.0%; the pH value of a high-purity tea saponin sodium product (1% water solution) is 6.2-6.4 by adopting a pH measuring method in the chemical industry standard HG/T4492-2013 natural non-ionic surfactant tea saponin of the people's republic of China.

Example 5

(1) crushing, sieving, soaking and removing iron: firstly, crushing defatted tea seed meal by using a stainless steel crusher and sieving the crushed defatted tea seed meal by using a 60-mesh standard sieve to obtain defatted tea seed meal powder; then adding 9kg of the obtained degreased tea seed meal into 63kg of softened water, stirring for 5 hours at room temperature, removing scrap iron in the mixture by using an iron remover after stirring is finished, and obtaining degreased tea seed meal soaking mixed liquor after scrap iron removal for later use;

(2) alkaline wall breaking and extraction:

A. adding sodium carbonate with the mass of 0.2% into the prepared degreasing tea seed meal soaking mixed liquid without the iron filings, stirring for 1 hour at 65 ℃, and obtaining mixed liquid A after stirring for later use;

B. under the condition of stirring, adjusting the pH value of the mixed solution A to 11.2 by using a sodium hydroxide solution, stirring for 1 hour at 65 ℃, and after the stirring is finished, performing centrifugal separation to obtain an extracting solution a1 and tea seed meal residue b1 for later use;

C. adding softened water with the mass 2.5 times of that of the tea seed meal residue B1 obtained in the step B, carrying out secondary extraction according to the method for primary extraction in the step B, and removing the precipitate to obtain an extracting solution a 2; mixing the extract a1 and the extract a2 to obtain an extract mixed solution for later use;

(3) oxidation, impurity solubilization and decolorization: under the condition of stirring, adding ozone with the mass of 0.05% into the extract mixed liquor obtained in the step II, and continuously stirring for 10 hours to obtain oxidation solubilization decolorant for later use;

(4) cooling, acid precipitation and water washing: under the condition of stirring, firstly reducing the temperature of the oxidation solubilization decolorization solution obtained in the step three to 15 ℃, then regulating the pH of the oxidation solubilization decolorization solution to 3.3 by using a hydrochloric acid solution, continuing stirring for 0.75 hour, performing centrifugal separation after the stirring is finished, and removing the supernatant to obtain an acidified crude tea saponin acid precipitate product; adding softened water with the mass 2 times of the crude acid precipitation product of the tea saponin, the temperature of which is 15 ℃ and the pH value of which is 3.3 into the crude acid precipitation product of the tea saponin, stirring for 1 hour for carrying out primary washing, carrying out centrifugal separation after the washing is finished, and removing supernatant to obtain the crude acid precipitation product of the tea saponin after the primary washing; and (4) carrying out secondary washing according to the primary washing method to obtain the acidified tea saponin acid precipitate crude product after water washing for later use.

(5) Dissolution, sodium treatment and impurity removal: adding an ethanol water solution with the mass of 75% and 3 times of that of the acidified tea saponin acid precipitation crude product obtained in the step four, heating the mixed solution to 35 ℃ under the condition of cooling and refluxing, stirring for 1 hour, performing centrifugal separation after stirring, and removing the precipitate to obtain an acidified ethanol-water solution of tea saponin acid; under the condition of stirring, adjusting the pH value of the acidified ethanol-water solution of the tea saponin acid to 5.8 by using a sodium hydroxide solution, continuously stirring for 1 hour, performing centrifugal separation after stirring, and removing the precipitate to obtain the ethanol-water solution of the tea saponin sodium for later use.

(6) Concentration and drying: concentrating and recovering ethanol in the ethanol-water solution of the sodium tea saponin prepared by the step fifthly by using a vacuum concentration method to obtain concentrated solution of the sodium tea saponin; drying the obtained concentrated solution of the tea saponin sodium until the water content is less than or equal to 5 percent, thus obtaining 0.99 kg of light yellow high-purity tea saponin sodium product.

The obtained high-purity tea saponin sodium product is light yellow powder, and the yield is 0.99/9-11.0%. Determining that the purity of the tea saponin of the obtained tea saponin sodium product is 96.9% by adopting an acid hydrolysis-acetone Soxhlet extraction-constant weight method in the chemical industry standard HG/T4492-2013 natural nonionic surfactant tea saponin, multiplying the purity by a conversion coefficient 1.018(1245.54/1223.54) to convert the tea saponin into the tea saponin sodium, wherein the purity of the tea saponin sodium of the obtained tea saponin sodium product is 98.6%; the pH value of a high-purity tea saponin sodium product (1% water solution) is 5.7-5.9 by adopting a pH measuring method in the chemical industry standard HG/T4492-2013 natural non-ionic surfactant tea saponin of the people's republic of China.

Example 6

(1) crushing, sieving, soaking and removing iron: firstly, crushing defatted tea seed meal by using a stainless steel crusher and sieving the crushed defatted tea seed meal by using a 80-mesh standard sieve to obtain defatted tea seed meal powder; adding 115kg of the obtained degreased tea seed meal into 1150kg of softened water, stirring for 3 hours at room temperature, removing iron filings in the mixture by using an iron remover after stirring is finished, and obtaining degreased tea seed meal soaking mixed liquid after iron filings removal for later use;

(2) alkaline wall breaking and extraction:

A. adding sodium carbonate with the mass of 0.75% into the prepared degreasing tea seed meal soaking mixed liquor without the iron filings, stirring for 1.5 hours at 75 ℃, and obtaining mixed liquor A after stirring for later use;

B. under the condition of stirring, adjusting the pH value of the mixed solution A to 11.4 by using a sodium hydroxide solution, stirring for 1.5 hours at the temperature of 60 ℃, and performing centrifugal separation after stirring to obtain an extracting solution a1 and tea seed meal residue b1 for later use;

C. adding softened water with the mass being 3.5 times of that of the tea seed meal residue B1 obtained in the step B, carrying out secondary extraction according to the method for primary extraction in the step B, and removing the precipitate to obtain an extracting solution a 2; mixing the extract a1 and the extract a2 to obtain an extract mixed solution for later use;

(3) oxidation, impurity solubilization and decolorization: under the condition of stirring, adding hydrogen peroxide with the mass of 0.35% into the extract mixed liquor obtained in the step II, and continuously stirring for 45 hours to obtain oxidation solubilization decolorant for later use;

(4) cooling, acid precipitation and water washing: under the condition of stirring, firstly reducing the temperature of the oxidation solubilization decolorization solution obtained in the step three to 10 ℃, then regulating the pH of the oxidation solubilization decolorization solution to 3.1 by using a hydrochloric acid solution, continuing stirring for 1.5 hours, carrying out centrifugal separation after the stirring is finished, and removing the supernatant to obtain an acidified tea saponin acid precipitate crude product; adding softened water with the temperature of 10 ℃ and the pH value of 3.1, the mass of which is 3 times that of the acidified tea saponin acid precipitation crude product, stirring for 1 hour for carrying out primary washing, carrying out centrifugal separation after the washing is finished, and removing supernatant to obtain the acidified tea saponin acid precipitation crude product after the primary washing; and (4) carrying out secondary washing according to the method of the primary washing to obtain the acidified tea saponin acid precipitate crude product after water washing for later use.

(5) Dissolution, sodium treatment and impurity removal: adding an ethanol water solution with the mass of 80% and 2.8 times of that of the water-washed acidified tea saponin acid precipitation crude product into the water-washed acidified tea saponin acid precipitation crude product, heating the mixed solution to 50 ℃ under the condition of cooling and refluxing, stirring for 2 hours, performing centrifugal separation after stirring, and discarding the precipitation to obtain an acidified ethanol-water solution of tea saponin acid; under the condition of stirring, adjusting the pH value of the acidified ethanol-water solution of the tea saponin acid to 6.35 by using a sodium hydroxide solution, continuously stirring for 3.5 hours, performing centrifugal separation after stirring is finished, and removing the precipitate to obtain the ethanol-water solution of the tea saponin sodium for later use.

(6) Concentration and drying: concentrating and recovering ethanol in the ethanol-water solution of the sodium tea saponin prepared in the step I by using a vacuum concentration method to obtain concentrated solution of the sodium tea saponin; drying the obtained concentrated solution of the sodium theasapogeninate until the percentage content of water is less than or equal to 5 percent, thus obtaining 15.5 kilograms of white high-purity sodium theasapogeninate products.

The obtained high-purity tea saponin sodium product is light yellow powder, and the yield is 15.5/115-13.5%. Determining that the purity of the tea saponin of the obtained tea saponin sodium product is 97.3% by adopting an acid hydrolysis-acetone Soxhlet extraction-constant weight method in the chemical industry standard HG/T4492-2013 natural nonionic surfactant tea saponin, multiplying the purity by a conversion coefficient 1.018(1245.54/1223.54) to convert the tea saponin into the tea saponin sodium, wherein the purity of the tea saponin sodium of the obtained tea saponin sodium product is 99.0%; the pH value of a high-purity tea saponin sodium product (1% water solution) is 6.25-6.45 by adopting a pH measuring method in the chemical industry standard HG/T4492-2013 natural non-ionic surfactant tea saponin of the people's republic of China.

Example 7

(1) crushing, sieving, soaking and removing iron: firstly, crushing defatted tea seed meal by using a stainless steel crusher and sieving the crushed defatted tea seed meal by using a 40-mesh standard sieve to obtain defatted tea seed meal powder; adding 228kg of the obtained degreased tea seed meal powder into 1596kg of softened water, stirring at room temperature for 3 hours, removing scrap iron in the mixture by using an iron remover after stirring is finished, and obtaining degreased tea seed meal soaking mixed liquid after the scrap iron is removed for later use;

(2) alkaline wall breaking and extraction:

A. adding sodium carbonate with the mass of 0.25% into the prepared degreasing tea seed meal soaking mixed liquid without the iron filings, stirring for 2 hours at 60 ℃, and obtaining mixed liquid A after stirring for later use;

B. under the condition of stirring, adjusting the pH value of the mixed solution A to 11.5 by using a sodium hydroxide solution, stirring for 2 hours at 60 ℃, and after the stirring is finished, performing centrifugal separation to obtain an extracting solution a1 and tea seed meal residue b1 for later use;

C. adding softened water with the mass being 4.5 times of that of the tea seed dregs B1 obtained in the step B, carrying out secondary extraction according to the method for the primary extraction in the step B, and removing the precipitate to obtain an extracting solution a 2; mixing the extract a1 and the extract a2 to obtain an extract mixed solution for later use;

(4) cooling, acid precipitation and water washing: under the condition of stirring, firstly reducing the temperature of the oxidation solubilization decolorization solution obtained in the step three to 0 ℃, then regulating the pH of the oxidation solubilization decolorization solution to 3.2 by using a hydrochloric acid solution, continuing stirring for 1.5 hours, carrying out centrifugal separation after the stirring is finished, and removing the supernatant to obtain an acidified tea saponin acid precipitate crude product; adding softened water with the mass of 3.5 times of that of the acid precipitated crude product of the tea saponin, the temperature of which is 0 ℃ and the pH value of which is 3.2 into the acid precipitated crude product of the tea saponin, stirring for 2 hours to carry out primary washing, carrying out centrifugal separation after the washing is finished, and removing supernatant to obtain the acid precipitated crude product of the tea saponin after the primary washing; and (4) carrying out secondary washing according to the method of the primary washing to obtain the acidified tea saponin acid precipitate crude product after water washing for later use.

(6) Concentration and drying: concentrating and recovering ethanol in the ethanol-water solution of the sodium tea saponin prepared by the step fifthly by using a vacuum concentration method to obtain concentrated solution of the sodium tea saponin; drying the obtained concentrated solution of the sodium theasapogenin to the water content of less than or equal to 5 percent to obtain 30.1 kg of white high-purity sodium theasapogenin product

The obtained high-purity tea saponin sodium product is light yellow powder, and the yield is 30.1/228-14.5%. Determining that the purity of the tea saponin of the obtained tea saponin sodium product is 97.5% by adopting an acid hydrolysis-acetone Soxhlet extraction-constant weight method in the chemical industry standard HG/T4492-2013 natural nonionic surfactant tea saponin, multiplying the purity by a conversion coefficient 1.018(1245.54/1223.54) to convert the tea saponin into the tea saponin sodium, wherein the purity of the tea saponin sodium of the obtained tea saponin sodium product is 99.2%; the pH value of a high-purity tea saponin sodium product (1% water solution) is 6.4-6.6 by adopting a pH measuring method in the chemical industry standard HG/T4492-2013 natural non-ionic surfactant tea saponin of the people's republic of China.

Example 8

(1) crushing, sieving, soaking and removing iron: firstly, crushing degreased tea seed meal by using a stainless steel crusher and sieving the degreased tea seed meal by using a 60-mesh standard sieve to obtain degreased tea seed meal; adding the obtained 250kg of degreased tea seed meal into 1500kg of softened water, stirring for 15 hours at room temperature, removing scrap iron in the mixture by using an iron remover after stirring is finished, and obtaining degreased tea seed meal soaking mixed liquor after scrap iron removal for later use;

(2) alkaline wall breaking and extraction:

A. adding sodium carbonate with the mass of 0.15% into the prepared degreasing tea seed meal soaking mixed liquor without the iron filings, stirring for 0.5 hour at 80 ℃, and obtaining mixed liquor A after stirring for later use;

B. under the condition of stirring, adjusting the pH value of the mixed solution A to 11.1 by using a sodium hydroxide solution, stirring at 80 ℃ for 0.5 hour, and after the stirring is finished, performing centrifugal separation to obtain an extracting solution a1 and tea seed meal residue b1 for later use;

(3) oxidation, impurity solubilization and decolorization: under the condition of stirring, adding 0.08% of ozone by mass into the extract mixed liquor obtained in the step II, and continuously stirring for 35 hours to obtain oxidation solubilization decolorant for later use;

(4) cooling, acid precipitation and water washing: under the condition of stirring, firstly reducing the temperature of the oxidation solubilization decolorization solution obtained in the step three to 20 ℃, then regulating the pH of the oxidation solubilization decolorization solution to 3.3 by using a hydrochloric acid solution, continuing stirring for 0.5 hour, performing centrifugal separation after the stirring is finished, and removing the supernatant to obtain an acidified tea saponin acid precipitate crude product; adding softened water with the mass of 3 times of the crude acid precipitation product of the tea saponin, the temperature of which is 20 ℃ and the pH value of which is 3.3 into the crude acid precipitation product of the tea saponin, stirring for 1 hour for carrying out primary washing, carrying out centrifugal separation after the washing is finished, and removing supernatant to obtain the crude acid precipitation product of the tea saponin after the primary washing; and (4) carrying out secondary washing according to the method of the primary washing to obtain the acidified tea saponin acid precipitate crude product after water washing for later use.

(5) Dissolution, sodium treatment and impurity removal: adding an ethanol water solution with the mass of 75% and 4.5 times of that of the water-washed acidified tea saponin acid precipitation crude product into the water-washed acidified tea saponin acid precipitation crude product, heating the mixed solution to 35 ℃ under the condition of cooling and refluxing, stirring for 0.5 hour, performing centrifugal separation after stirring, and discarding the precipitation to obtain an acidified ethanol-water solution of tea saponin acid; under the condition of stirring, adjusting the pH value of the acidified ethanol-water solution of the tea saponin acid to 5.6 by using a sodium hydroxide solution, continuously stirring for 0.5 hour, performing centrifugal separation after stirring is finished, and removing the precipitate to obtain the ethanol-water solution of the tea saponin sodium for later use.

(6) Concentration and drying: concentrating and recovering ethanol in the ethanol-water solution of the sodium tea saponin prepared by the step fifthly by using a vacuum concentration method to obtain concentrated solution of the sodium tea saponin; and drying the obtained concentrated solution of the sodium theasapogeninate until the percentage content of water is less than or equal to 5 percent, thereby obtaining 35kg of white high-purity sodium theasapogeninate product.

The obtained high-purity tea saponin sodium product is light yellow powder, and the yield is 35/250-14.0%. Determining that the purity of the tea saponin of the obtained tea saponin sodium product is 97.2% by adopting an acid hydrolysis-acetone Soxhlet extraction-constant weight method in the chemical industry standard HG/T4492-2013 natural nonionic surfactant tea saponin, multiplying the purity by a conversion coefficient 1.018(1245.54/1223.54) to convert the tea saponin into the tea saponin sodium, wherein the purity of the tea saponin sodium of the obtained tea saponin sodium product is 98.9%; the pH value of a high-purity tea saponin sodium product (1% water solution) is 5.5-5.7 by adopting a pH measuring method in the chemical industry standard HG/T4492-2013 natural non-ionic surfactant tea saponin of the people's republic of China.

Example 9

(1) crushing, sieving, soaking and removing iron: firstly, crushing degreased tea seed meal by using a stainless steel crusher and sieving the degreased tea seed meal by using a 60-mesh standard sieve to obtain degreased tea seed meal; adding 350kg of the obtained degreased tea seed meal powder into 2880kg of softened water, stirring for 6 hours at room temperature, removing scrap iron in the mixture by using an iron remover after stirring is finished, and obtaining degreased tea seed meal soaking mixed liquor after the scrap iron is removed for later use;

(2) alkaline wall breaking and extraction:

A. adding sodium carbonate with the mass of 0.45% into the prepared degreasing tea seed meal soaking mixed liquid without the iron filings, stirring for 1 hour at 60 ℃, and obtaining mixed liquid A after stirring for later use;

(4) cooling, acid precipitation and water washing: under the condition of stirring, firstly reducing the temperature of the oxidation solubilization decolorization solution obtained in the step three to 15 ℃, then regulating the pH of the oxidation solubilization decolorization solution to 3.1 by using a hydrochloric acid solution, continuing stirring for 0.5 hour, performing centrifugal separation after the stirring is finished, and removing the supernatant to obtain an acidified crude tea saponin acid precipitate product; adding softened water with the mass of 3 times of that of the acid precipitation crude product of the tea saponin, the temperature of which is 15 ℃ and the pH value of which is 3.1 into the acid precipitation crude product of the tea saponin, stirring for 1 hour for carrying out primary washing, carrying out centrifugal separation after the washing is finished, and removing supernatant to obtain the acid precipitation crude product of the tea saponin after the primary washing; and (4) carrying out secondary washing according to the method of the primary washing to obtain the acidified tea saponin acid precipitate crude product after water washing for later use.

(5) Dissolving, sodium treatment and impurity removal: adding an ethanol water solution with the mass of 80% and 5 times of that of the acidified tea saponin acid precipitation crude product obtained in the step four, heating the mixed solution to 35 ℃ under the condition of cooling and refluxing, stirring for 2 hours, performing centrifugal separation after stirring, and removing the precipitate to obtain an acidified ethanol-water solution of tea saponin acid; under the condition of stirring, adjusting the pH value of the acidified ethanol-water solution of the tea saponin acid to 6 by using a sodium hydroxide solution, continuously stirring for 2.5 hours, performing centrifugal separation after stirring is finished, and removing the precipitate to obtain the ethanol-water solution of the tea saponin sodium for later use.

(6) Concentration and drying: concentrating and recovering ethanol in the ethanol-water solution of the sodium tea saponin prepared by the step fifthly by using a vacuum concentration method to obtain concentrated solution of the sodium tea saponin; drying the obtained concentrated solution of the sodium theasapogeninate until the percentage content of water is less than or equal to 5 percent, thus obtaining 49.4 kg of white high-purity sodium theasapogeninate product.

The obtained high-purity tea saponin sodium product is light yellow powder, and the yield is 49.4/350-14.1%. Determining that the purity of the tea saponin of the obtained tea saponin sodium product is 97.5% by adopting an acid hydrolysis-acetone Soxhlet extraction-constant weight method in the chemical industry standard HG/T4492-2013 natural nonionic surfactant tea saponin, multiplying the purity by a conversion coefficient 1.018(1245.54/1223.54) to convert the tea saponin into the tea saponin sodium, wherein the purity of the tea saponin sodium of the obtained tea saponin sodium product is 99.3%; the pH value of a high-purity tea saponin sodium product (1% water solution) is 5.9-6.1 by adopting a pH measuring method in the chemical industry standard HG/T4492-2013 natural non-ionic surfactant tea saponin of the people's republic of China.

Example 10

(1) crushing, sieving, soaking and removing iron: firstly, crushing defatted tea seed meal by using a stainless steel crusher and sieving the crushed defatted tea seed meal by using a 100-mesh standard sieve to obtain defatted tea seed meal powder; then adding 435kg of the obtained degreased tea seed meal powder into 4350kg of softened water, stirring for 3.5 hours at room temperature, removing iron chips in the mixture by using an iron remover after stirring is finished, and obtaining degreased tea seed meal soaking mixed liquid after the iron chips are removed for later use;

(2) alkaline wall breaking and extraction:

A. adding sodium carbonate with the mass of 0.85% of that of the degreased tea seed meal soaking mixed liquor which is prepared in the step I and is subjected to scrap iron removal, stirring for 2 hours at 75 ℃, and obtaining mixed liquor A after stirring is finished for later use;

B. under the condition of stirring, adjusting the pH value of the mixed solution A to 11.1 by using a sodium hydroxide solution, stirring for 2 hours at 75 ℃, and after stirring, performing centrifugal separation to obtain an extracting solution a1 and tea seed meal residue b1 for later use;

C. adding softened water 2 times the mass of the tea seed meal residue B1 obtained in the step B, carrying out secondary extraction according to the method for primary extraction in the step B, and removing the precipitate to obtain an extracting solution a 2; mixing the extract a1 and the extract a2 to obtain an extract mixed solution for later use;

(3) oxidation, impurity solubilization and decolorization: under the condition of stirring, adding hydrogen peroxide with the mass of 0.15% into the extract mixed liquor obtained in the step II, and continuously stirring for 15 hours to obtain oxidation solubilization decolorant for later use;

(4) cooling, acid precipitation and water washing: under the condition of stirring, firstly reducing the temperature of the oxidation solubilization decolorization solution obtained in the step three to 5 ℃, then regulating the pH of the oxidation solubilization decolorization solution to 3.3 by using a hydrochloric acid solution, continuing stirring for 1 hour, performing centrifugal separation after the stirring is finished, and removing the supernatant to obtain an acidified tea saponin acid precipitation crude product; adding softened water with the mass of 3 times of that of the acid precipitation crude product of the tea saponin, the temperature of which is 5 ℃ and the pH value of which is 3.3 into the acid precipitation crude product of the tea saponin, stirring for 2 hours to carry out primary washing, carrying out centrifugal separation after the washing is finished, and removing supernatant to obtain the acid precipitation crude product of the tea saponin after the primary washing; and (4) carrying out secondary washing according to the method of the primary washing to obtain the acidified tea saponin acid precipitate crude product after water washing for later use.

(5) Dissolving, sodium treatment and impurity removal: adding an ethanol water solution with the mass of 75% and 3.5 times of that of the water-washed acidified tea saponin acid precipitation crude product into the water-washed acidified tea saponin acid precipitation crude product, heating the mixed solution to 50 ℃ under the condition of cooling and refluxing, stirring for 2.5 hours, performing centrifugal separation after stirring, and discarding the precipitation to obtain an acidified ethanol-water solution of tea saponin acid; under the condition of stirring, adjusting the pH value of the acidified ethanol-water solution of the tea saponin acid to 6.45 by using a sodium hydroxide solution, continuously stirring for 1 hour, performing centrifugal separation after stirring, and removing the precipitate to obtain the ethanol-water solution of the tea saponin sodium for later use.

(6) Concentration and drying: concentrating and recovering ethanol in the ethanol-water solution of the sodium tea saponin prepared by the step fifthly by using a vacuum concentration method to obtain concentrated solution of the sodium tea saponin; drying the obtained concentrated solution of the tea saponin sodium until the water content is less than or equal to 5 percent, thus obtaining 59.6 kilograms of light yellow high-purity tea saponin sodium product.

The obtained high-purity tea saponin sodium product is light yellow powder, and the yield is 59.6/435-13.7%. Determining that the purity of the tea saponin of the obtained tea saponin sodium product is 96.6% by adopting an acid hydrolysis-acetone Soxhlet extraction-constant weight method in the chemical industry standard HG/T4492-2013 natural nonionic surfactant tea saponin, multiplying the purity by a conversion coefficient 1.018(1245.54/1223.54) to convert the tea saponin into the tea saponin sodium, wherein the purity of the tea saponin sodium of the obtained tea saponin sodium product is 98.3%; the pH of a high-purity tea saponin sodium product (1% aqueous solution) is 6.35-6.55 by adopting a pH measuring method in the chemical industry standard HG/T4492-2013 natural non-ionic surfactant tea saponin of the people's republic of China.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims

1. A preparation method of high-purity tea saponin sodium is characterized by comprising the following steps:

(2) alkaline wall breaking and extraction:

adding sodium carbonate into the degreased tea seed meal soaking mixed liquid which is prepared in the step of removing the iron filings, stirring for 0.5-2.0 hours at the temperature of 60-80 ℃, and obtaining mixed liquid A after stirring for later use;

b, under the stirring condition, adjusting the pH value of the mixed solution A to 11.1-11.5 by using a sodium hydroxide solution, stirring for 0.5-2.0 hours at the temperature of 60-80 ℃, and performing centrifugal separation after stirring to obtain an extracting solution a1 and tea seed meal residue B1 for later use;

c, adding softened water into the tea seed meal residue B1 obtained in the step B, carrying out secondary extraction according to the method for the primary extraction in the step B, and removing the precipitate to obtain an extracting solution a 2; mixing the extract a1 and the extract a2 to obtain an extract mixed solution for later use;

(4) cooling, acid precipitation and water washing: under the condition of stirring, firstly reducing the temperature of the oxidation solubilization decolorization solution obtained in the step three to 0-20 ℃, then adjusting the pH of the oxidation solubilization decolorization solution to 3.1-3.3 by using a hydrochloric acid solution, continuously stirring for 0.5-1.5 hours, performing centrifugal separation after stirring, and removing supernatant to obtain an acidified tea saponin acid precipitate crude product; adding softened water with the temperature of 0-20 ℃ and the pH of 3.1-3.3 into the acidified tea saponin acid precipitation crude product, stirring for 1.0-2.0 hours for first washing, performing centrifugal separation after stirring, and removing supernatant to obtain the acidified tea saponin acid precipitation crude product after the first washing; washing for the second time according to the first washing method to obtain an acidified tea saponin acid precipitate crude product after washing for later use;

(5) dissolving, sodium treatment and impurity removal: adding an ethanol water solution into the water-washed acidified tea saponin acid precipitation crude product obtained in the step four, heating the mixed solution to 30-50 ℃ under the condition of cooling and refluxing, stirring for 0.5-2.5 hours, performing centrifugal separation after stirring, and removing the precipitate to obtain an ethanol-water solution of acidified tea saponin acid; under the condition of stirring, adjusting the pH value of the acidified ethanol-water solution of the tea saponin acid to 5.5-6.5 by using a sodium hydroxide solution, continuously stirring for 0.5-3.5 hours, performing centrifugal separation after stirring, and removing the precipitate to obtain the ethanol-water solution of the tea saponin sodium for later use;

2. The preparation method of high-purity sodium theasapogenin according to claim 1, wherein the preparation method comprises the following steps: the method comprises the steps of squeezing tea seed meal obtained after tea seed oil is squeezed from tea seeds through a squeezing method, and removing residual oil in the squeezed tea seed meal through a leaching method to obtain the tea seed meal with the oil content less than or equal to 1.0%; the iron remover is used in food industry or chemical industry; the mass ratio of the degreased tea seed meal to the softened water is 1: 6-10; the stirring and soaking time is 2-20 hours.

3. The preparation method of high-purity sodium theasapogenin according to claim 1, wherein the preparation method comprises the following steps: the sodium carbonate is industrial grade, chemically pure or analytically pure sodium carbonate; the sodium hydroxide is industrial grade, chemically pure or analytically pure sodium hydroxide.

4. The preparation method of high-purity sodium theasapogenin according to claim 1, wherein the preparation method comprises the following steps: in the step A, the mass ratio of the mixed solution of the degreased tea seed meal soaked with the iron scraps in the step B to the sodium carbonate is 100:0.05-1, and the mass ratio of the tea seed meal b1 to the softened water in the step C is 1: 1.5-4.5.

5. The preparation method of high-purity sodium theasapogenin according to claim 1, wherein the preparation method comprises the following steps: the traceless oxidant in the step three is industrial, chemically pure or analytically pure hydrogen peroxide or ozone water prepared by an ozone generator;

the mass ratio of the extracting solution mixed solution to the traceless oxidant is 100: 0.001-0.5.

6. The preparation method of high-purity sodium theasapogenin according to claim 1, wherein the preparation method comprises the following steps: the hydrochloric acid in the fourth step is industrial grade, chemically pure or analytically pure hydrochloric acid; the mass ratio of the acidified crude tea saponin acid precipitate product to the softened water is 1: 1.5-3.5.

7. The preparation method of high-purity sodium theasapogenin according to claim 1, wherein the preparation method comprises the following steps: in the step (5), the volume percentage of the ethanol in the ethanol water solution is 75-80%, and the mass ratio of the acidified tea saponin acid precipitate crude product after water washing to the ethanol water solution is 1: 2.5-5.5.

8. The preparation method of high-purity sodium theasapogenin according to claim 1, wherein the preparation method comprises the following steps: the ethanol in the step fifthly is industrial grade, chemically pure or analytically pure ethanol; the sodium hydroxide is industrial grade, chemically pure or analytically pure sodium hydroxide.

9. The preparation method of high-purity sodium theasapogenin according to claim 1, wherein the preparation method comprises the following steps: the step sixteenth of four is dried under normal pressure, vacuum or spray.