High-purity camellia saponin and extraction method thereof

Abstract

The application discloses high-purity oil tea saponin and an extraction method thereof, and comprises the following steps: crushing oil tea seed cake or tea leaf seed cake, using a low-grade alcohol solution containing water to perform dynamic countercurrent extraction on the crushed oil tea seed cake or tea leaf seed cake, and collecting a filtrate; concentrating and recovering alcohol from the filtrate until the alcohol content in the concentrated solution is less than 3 wt%, and obtaining concentrated solution A; diluting the concentrated solution A with water, treating the dilution liquid through an ultrafiltration membrane, concentrating the ultrafiltration membrane permeate liquid through a nanofiltration membrane, and obtaining concentrated solution B; adding water to the concentrated solution to obtain a dissolution liquid, decolorizing the dissolution liquid, adsorbing the decolorized liquid through a macroporous adsorption resin, and then resolving the macroporous adsorption resin through an ethanol solution to obtain a resolution liquid; and concentrating, sterilizing, filtering and drying the resolution liquid to obtain oil tea saponin. The oil tea saponin prepared by the application has high purity, low impurity content and light color, is widely applied to high-end washing and protecting products, cosmetics and other industries, and the preparation method is simple and feasible, and is suitable for large-scale production.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of biological extraction, in particular to a high-purity tea saponin and an extraction method thereof. BACKGROUND

[0002] Tea saponin, also known as tea saponin, is a kind of glycoside compound extracted from tea seed (tea seed, tea leaf seed), which is a good natural surfactant. It can be widely used in light industry, chemical industry, pesticide, feed, breeding, textile, oil extraction, mining, building materials and highway construction fields.

[0003] The tea saponin prepared by the prior art contains various impurities such as protein, polysaccharide, flavone, polyphenol, organic acid, tannin, tannin, pigment and the like, which affects the performance stability and product formula advantage of the tea saponin, seriously affects the unique surface activity function and the effect of inhibiting bacteria and removing dandruff of the tea saponin, and can only be used in the fields of pesticide adjuvant, low-end detergent, oil extraction and building materials. The refined and purified tea saponin needs to further remove the impurities such as protein, tea polysaccharide, flavone, polyphenol, organic acid, tannin, tannin and other pigments in the crude saponin, especially the colored impurities, which is the key and difficulty of the preparation of high-purity tea saponin. The existing refining and purification methods include flocculation, precipitation, resin adsorption, hydrogen peroxide oxidation or repeated recrystallization, etc. However, these refining and purification methods have the problems of poor impurity removal effect, complex process, large loss of tea saponin, introduction of new chemical pollutants which are difficult to completely remove, and are not suitable for large-scale industrial production. SUMMARY

[0004] Therefore, the present application aims to provide a high-purity tea saponin and an extraction method thereof. The high-purity tea saponin has high purity, low impurity content and light color, and can be widely used in high-end washing and care products, cosmetics, pharmaceuticals and food industry. The preparation method is simple and feasible, and is suitable for large-scale industrial production.

[0005] In a first aspect, the present application provides an extraction method of high-purity tea saponin, comprising the following steps:

[0006] The tea seed cake or tea leaf seed cake is crushed, and a low-grade alcohol solution containing water is used to perform dynamic countercurrent extraction on the crushed tea seed cake, and the filtrate is collected;

[0007] The filtrate is concentrated to recover alcohol, and the alcohol content in the concentrated solution is less than 3wt%, to obtain a concentrated solution A;

[0008] The concentrated solution A is diluted with water, and the diluted solution is treated by an ultrafiltration membrane. The permeate of the ultrafiltration membrane is concentrated by a nanofiltration membrane to obtain a concentrated solution B;

[0009] Water is added to the concentrated solution B to obtain a dissolving solution, the dissolving solution is decolorized, the decolorized solution is adsorbed by a macroporous adsorption resin, and then the macroporous adsorption resin is eluted by an ethanol solution to obtain an eluted solution;

[0010] The eluted solution is concentrated, sterilized, filtered and dried to obtain the tea saponin.

[0011] Compared with the prior art, the preparation method of the present application first crushes the oil tea seed cake or tea seed cake, and then performs dynamic countercurrent extraction on the crushed oil tea seed cake or tea seed cake to obtain a filtrate; then the filtrate is concentrated, the concentrated solution is diluted with water, the diluted solution is treated by ultrafiltration membrane, and the permeate of the ultrafiltration membrane is concentrated by nanofiltration membrane to effectively remove macromolecular substances and small molecular inorganic salts; then water is added to the concentrated solution to dissolve, decolorize, adsorb the decolorized solution by resin, and elute by ethanol to further improve the purity of the tea saponin; finally, the eluted solution is treated to obtain high-purity tea saponin. The preparation method of the high-purity tea saponin of the present application can prepare high-purity tea saponin with high purity, low impurity content and light color, which can be widely used in high-end washing and protection products, cosmetics, pharmaceuticals and food industries, and the preparation method is simple and feasible, and suitable for large-scale industrial production.

[0012] Further, the crushing conditions of the oil tea seed cake or tea seed cake are as follows: the feeding speed is 10-200 kg / h, and the frequency is 30-50 HZ; the particle size of the crushed oil tea seed cake or tea seed cake is 0.1-2 mm; when the crushed oil tea seed cake or tea seed cake is subjected to dynamic countercurrent extraction, the extraction temperature is 30-50 DEG C, the extraction frequency is 30-50 HZ, and the extraction advancing speed is 5-10 m / h; the aqueous low-alcohol solution comprises low-alcohol, compounded salt and water, wherein the mass concentration of the low-alcohol is 50-90%, and the mass concentration of the compounded salt is 0.1-0.5%; the compounded salt comprises one or more of sulfite, bisulfite or pyrosulfite.

[0013] Compared with the prior art, the preparation method of the present application uses an aqueous low-alcohol solution containing 0.1-0.5 wt% of sulfite, bisulfite or pyrosulfite to replace water or an alcohol solution not containing the above compounded salt in the prior art, which can reduce the exudation of oil, protein and macromolecular tannins in raw material extraction, make it easier to filter, reduce the further oxidation of part of phenolic compounds in the extraction process, reduce the increase of color-developing substances, prevent the deepening of the color of the material liquid, and reduce the burden of product decolorization.

[0014] Further, the method for recovering alcohol by concentrating the filtrate is nanofiltration membrane concentration, wherein the specification of the nanofiltration membrane is 150-200 Da, the pressure during the operation of the nanofiltration membrane is 0.5-3.0 MPa, the temperature is 10-65 DEG C, the pH is 3.0-12.0, and the flow rate of the filtrate is 0.5-5.0 m 3 / h.

[0015] Further, the Brix value of the dilute solution obtained by diluting the concentrated solution A with water is 1-10%; when the dilute solution is treated by ultrafiltration membrane, the specification of the ultrafiltration membrane is 15-20 KDa, the inlet membrane pressure during operation is 0.1-1.0 MPa, the temperature is 10-65℃, the pH is 3.0-12.0, the flow rate of the dilute solution is 0.5-5.0 m3 / h, the molecular weight cut-off is greater than 20 KDa, and water is added continuously for dialysis until the Brix value of the permeate is ≤0.5%; when the ultrafiltration membrane permeate is concentrated by nanofiltration membrane, the specification of the nanofiltration membrane is 400-600 Da, the pressure during operation is 0.1-3.0 MPa, the temperature is 10-65℃, the pH is 3.0-12.0, and the flow rate of the ultrafiltration membrane permeate is 0.5-5.0 m3 / h, until the Brix value of the concentrated solution is 25-30%, to obtain the concentrated solution B.

[0016] Further, the method for decolorizing the dissolved solution is adsorption by macroporous adsorption resin or ion exchange by anion exchange resin; when the dissolved solution is adsorbed by the macroporous adsorption resin or ion exchanged by the anion exchange resin, the loading speed of the dissolved solution is 0.5-1 BV / h, and the loading amount is 0.5-5.0 BV of the volume of the resin; the decolorized solution is obtained after the macroporous adsorption resin or the anion exchange resin is decolorized; the macroporous adsorption resin is polystyrene macroporous adsorption resin or acrylate macroporous adsorption resin, and the anion exchange resin is polystyrene skeleton or acrylate skeleton anion exchange resin.

[0017] Further, when the decolorized solution is adsorbed by the macroporous adsorption resin, the loading speed of the decolorized solution is 1-2 BV / h, and the loading amount is 0.5-5.0 BV of the volume of the resin; when the ethanol solution is eluted, the loading speed of the ethanol solution is 0.5-1 BV / h, and the loading amount is 1.0-5.0 BV.

[0018] Further, the method for concentrating the eluted solution is: the eluted solution is concentrated by membrane, and when the solid content of the concentrated solution reaches 20-30%, the single-effect external circulation concentrator is used for continuous concentration until the Brix value reaches 40-50%; the specification of the membrane used for membrane concentration is 100-200 Da; when the single-effect external circulation concentrator is used for continuous concentration, the concentration vacuum degree is 0.05-0.095 MPa, and the concentration temperature is 50-85℃.

[0019] Further, the sterilization temperature is 80-85℃, and the sterilization time is 30-35 min.

[0020] Further, the drying method is spray drying, the feed rate of the spray drying is 10-100 L / h, the inlet air temperature is 180-190℃, and the outlet air temperature is 85-90℃.

[0021] In a second aspect, the present application provides a high-purity oil tea saponin, the purity of the high-purity oil tea saponin is more than 97%, the protein content in the high-purity oil tea saponin is less than or equal to 1.0 wt%, the polyphenol content is less than or equal to 1.0 g / kg, and the absorbance Abs at a wavelength of 420-610 nm is less than 0.06.

[0022] Compared with the prior art, the high-purity oil tea saponin has the same beneficial effects as the oil tea saponin preparation method described above, which will not be repeated here. DETAILED DESCRIPTION

[0023] In order to make the technical problems to be solved by the present application, the technical solutions and beneficial effects more clear and explicit, the present application will be further described in detail below in combination with specific embodiments. It should be understood that the specific embodiments described here are only used to explain the present application, and are not used to limit the present application.

[0024] The present application provides a high-purity oil tea saponin extraction method, comprising the following steps:

[0025] The oil tea seed cake or tea seed cake is crushed, and a low-grade alcohol solution containing water is used to dynamically countercurrently extract the crushed oil tea seed cake or tea seed cake, and the filtrate is collected;

[0026] The filtrate is concentrated to recover alcohol, and the alcohol content in the concentrated solution is less than 3 wt%, to obtain concentrated solution A;

[0027] The concentrated solution A is diluted with water, and the dilution liquid is treated by ultrafiltration membrane, and the ultrafiltration membrane permeate is concentrated by nanofiltration membrane, to obtain concentrated solution B;

[0028] Water is added to the concentrated solution B to obtain a dissolved solution, the dissolved solution is decolorized, and the decolorized solution is adsorbed by a macroporous adsorption resin, and then eluted by an ethanol solution to obtain an eluted solution;

[0029] The eluted solution is concentrated, sterilized, filtered and dried to obtain oil tea saponin.

[0030] The preparation method of the application first crushes the oil tea seed cake or tea seed cake, uses a low-level alcohol solution containing water to dynamically countercurrently extract the crushed oil tea seed cake or tea seed cake, obtains a filtrate, and can fully extract the oil tea saponin in the oil tea seed cake or tea seed cake; then concentrates the filtrate to remove the alcohol in the filtrate; water-dilutes the obtained concentrated liquid A and performs ultrafiltration membrane treatment to effectively remove high-molecular and large-molecular proteins, oil tea polysaccharides, starch and large-molecular substances in the dilution liquid; then concentrates the ultrafiltration membrane permeate liquid through a nanofiltration membrane to obtain concentrated liquid B, further removes small-molecular inorganic salts in the ultrafiltration membrane permeate liquid, and the purity of the obtained concentrated liquid B is greatly improved; then water-dissolves the concentrated liquid B, decolorizes, performs resin adsorption on the decolorized liquid, and ethanol elution to obtain an elution liquid, removes colored substances and impurities in the oil tea saponin, and further improves the purity of the oil tea saponin; finally, processes the elution liquid to obtain high-purity oil tea saponin. The preparation method of the high-purity oil tea saponin makes the prepared high-purity oil tea saponin have high purity, low impurity content and light color, can be widely applied to high-end washing and protection products, cosmetics, medicines and food industries, and the preparation method is simple and feasible, and is suitable for large-scale industrial production.

[0031] In some embodiments, the crushing conditions of the oil tea seed cake or tea seed cake are as follows: the feeding speed is 10-200 kg / h, and the frequency is 30-50 HZ; the particle size of the crushed oil tea seed cake or tea seed cake is 0.1-2 mm; when the crushed oil tea seed cake or tea seed cake is dynamically countercurrently extracted, the extraction temperature is 30-50 DEG C, the extraction frequency is 30-50 HZ, and the extraction advancing speed is 5-10 m / h; the low-level alcohol solution containing water includes low-level alcohol, compounded salt and water, wherein the mass concentration of the low-level alcohol is 50-90%, the mass concentration of the compounded salt is 0.1-0.5%, and preferably 0.2-0.4%; the compounded salt includes one or more of sulfite, bisulfite or pyrosulfite. The low-level alcohol in the low-level alcohol solution containing water can be methanol, ethanol, n-propanol, isopropanol and n-butanol, etc.; the sulfite, bisulfite or pyrosulfite can be mixed in any mass ratio, and finally the content requirement in the low-level alcohol solution containing water is met; preferably, the mass ratio of the sulfite, bisulfite and pyrosulfite can be (1-2):(1-2):(2-3).

[0032] Specifically, the feeding speed of the crushed oil tea seed cake or tea seed cake can be 10 kg / h, 50 kg / h, 100 kg / h, 160 kg / h, 200 kg / h; the frequency can be 30 HZ, 35 HZ, 40 HZ, 45 HZ, 50 HZ; the particle size of the crushed oil tea seed cake or tea seed cake can be 0.1 mm, 0.6 mm, 1.0 mm, 1.6 mm, 2 mm; the extraction temperature of the crushed oil tea seed cake or tea seed cake can be 30°C, 33°C, 38°C, 45°C, 50°C; the extraction frequency can be 30 HZ, 35 HZ, 40 HZ, 42 HZ, 50 HZ, and the extraction advancing speed can be 5 m / h, 8 m / h, 8.5 m / h, 9 m / h, 10 m / h.

[0033] Under the cooperation of the above parameters and the aqueous lower alcohol solution, the oil tea saponin in the oil tea seed cake or tea seed cake can be fully extracted by crushing and extracting the oil tea seed cake or tea seed cake. The aqueous lower alcohol solution contains 0.1-0.5wt% of one or more of sulfite, bisulfite or pyrosulfite, which can reduce the exudation of oil, protein and macromolecular tannins in raw material extraction, make it easier to filter, reduce the further oxidation of part of phenolic compounds in the extraction process, reduce the increase of color developing substances, prevent the deepening of the color of the feed liquid, and reduce the burden of product discoloration.

[0034] In some embodiments, the method for concentrating and recovering alcohol from the filtrate is nanofiltration membrane concentration, wherein the specification of the nanofiltration membrane is 150-200 Da, the pressure is 0.5-3.0 MPa, the temperature is 10-65°C, the pH is 3.0-12.0, and the flow rate of the filtrate is 0.5-5.0 m 3 / h.

[0035] Specifically, the specification of the nanofiltration membrane can be 150 Da, 165 Da, 185 Da, 190 Da, 200 Da, the pressure can be 0.5 MPa, 0.9 MPa, 1.5 MPa, 2.5 MPa, 3 MPa, the temperature can be 10°C, 20°C, 35°C, 50°C, 65°C, the pH can be 3, 4, 5, 9, 12, and the flow rate of the filtrate can be 0.5 m 3 / h, 1.6 m 3 / h, 2.5 m 3 / h, 3.8 m 3 / h, 5 m 3 / h.

[0036] When the filtrate is concentrated by nanofiltration membrane, the filtrate can be fully concentrated under the above parameter conditions, and the alcohol in the filtrate can be removed. In actual operation, the recovered alcohol after concentration can be subjected to rectification treatment and recycled.

[0037] In some embodiments, after the concentrated solution A is diluted with water, the Brix value of the diluted solution is 1-10%; when the diluted solution is treated by the ultrafiltration membrane, the specification of the ultrafiltration membrane is 15-20KDa, the inlet membrane pressure during operation is 0.1-1.0MPa, the temperature is 10-65℃, the pH is 3.0-12.0, the flow rate of the diluted solution is 0.5-5.0m3 / h, macromolecular substances with a molecular weight greater than 20KDa are intercepted, and water is added for dialysis constantly until the Brix value of the permeate is ≤0.5% to end; when the ultrafiltration membrane permeate is concentrated by the nanofiltration membrane, the specification of the nanofiltration membrane is 400-600Da, the nanofiltration membrane can allow substances with a molecular weight less than 400Da to pass through and intercept substances with a molecular weight greater than 600Da, the pressure during operation is 0.1-3.0MPa, the temperature is 10-65℃, the pH is 3.0-12.0, the flow rate of the ultrafiltration membrane permeate is 0.5-5.0m3 / h, until the Brix value of the concentrated solution is 25-30% to end, and the concentrated solution B is obtained.

[0038] It should be noted that the Brix value refers to the content of soluble solids in the liquid. Specifically, after the concentrated solution A is diluted with water, the Brix value can be 1%, 3%, 6%, 8%, 10%; the specification of the ultrafiltration membrane can be 15KDa, 17KDa, 18KDa, 19KDa, 20KDa; the inlet membrane pressure during operation can be 0.1MPa, 0.3MPa, 0.5MPa, 0.8MPa, 1.0MPa; the temperature can be 10℃, 25℃, 37℃, 50℃, 65℃; the pH is 3, 5, 7, 9, 12; the flow rate of the diluted solution can be 0.5m 3 / h, 1.6m 3 / h, 3.0m 3 / h, 3.8m 3 / h, 5m 3 / h; when the treatment of the diluted solution by the ultrafiltration membrane ends, the Brix value of the permeate can be 0.1%, 0.2%, 0.35%, 0.4%, 0.5%. When the ultrafiltration membrane permeate is concentrated by the nanofiltration membrane, the specification of the nanofiltration membrane can be 400Da, 460Da, 500Da, 550Da, 600Da, the pressure during operation can be 0.1MPa, 0.8MPa, 1.5MPa, 2.0MPa, 3.0MPa; the temperature can be 10℃, 25℃, 37℃, 50℃, 65℃; the pH is 3, 6, 8, 10, 12; the flow rate of the diluted solution can be 0.5m 3 / h, 1.6m 3 / h, 3.0m 3 / h, 3.8m 3 / h, 5m 3 / h; the Brix value of the concentrated solution B can be 25%, 26.5%, 27.5%, 28%, 30%.

[0039] Under the above film specifications and parameter conditions, the high molecular and macromolecular protein, oil tea polysaccharide, starch, macromolecular substance and small molecule inorganic salt in the diluent are fully removed, and the purity of the oil tea saponin in the diluent is improved.

[0040] In some embodiments, the Brix value of the dissolving solution is 8-10%; the method for decolorizing the dissolving solution is adsorption by macroporous adsorption resin or ion exchange by anion exchange resin; when the dissolving solution is decolorized by macroporous adsorption resin or ion exchange by anion exchange resin, the loading speed of the dissolving solution is 0.5-1 BV / h, the loading amount is 0.5-5.0 BV of the volume of the resin, and the decolorized solution is obtained after the decolorization by macroporous adsorption resin or ion exchange by anion exchange resin is completed; the macroporous adsorption resin is weakly polar to polar macroporous resin with a particle size of 250 μm-1.25 mm, which can be polystyrene macroporous adsorption resin or acrylic ester macroporous adsorption resin; the anion exchange resin is weakly basic anion resin with a particle size of 250 μm-2 mm, which can be polystyrene skeleton or acrylic ester skeleton anion exchange resin.

[0041] Specifically, the Brix value of the dissolving solution can be 8%, 8.3%, 9%, 9.5%, 10%; the loading speed of the dissolving solution can be 0.5 BV / h, 0.65 BV / h, 0.7 BV / h, 0.9 BV / h, 1.0 BV / h; the loading amount can be 0.5 BV, 0.9 BV, 2.5 BV, 3.8 BV, 5.0 BV of the volume of the resin; the macroporous adsorption resin used for decolorizing the dissolving solution can be any one or more of ADS-7, DA201, DM100, LKS03, LKS11, MN100, MN270, SD331, SD333, T19, and XDA-8; the anion exchange resin used for decolorizing the dissolving solution can be any one or more of LX600J, D941, D900, D318, D301, D285, D201, and H280.

[0042] When the dissolving solution is decolorized, the colored substances in the dissolving solution can be effectively removed under the above parameter conditions, and the decolorized solution is more pure. It should be noted that the conventional technical means for decolorizing the solution in the prior art can be used for decolorizing the dissolving solution, as long as the purpose of decolorization can be achieved. The present application preferably uses macroporous adsorption resin adsorption decolorization or anion exchange resin ion exchange decolorization. It should be understood that during the macroporous adsorption resin adsorption decolorization or anion exchange resin ion exchange decolorization of the dissolving solution, the clear water flowing out at the beginning after the dissolving solution is loaded should be removed, and the collection starts when the feed liquid flows out. After the loading is completed, 1-5 wt% salt water can be used for cleaning, and the feed liquid and the cleaning liquid are collected to obtain the decolorized solution. As can be seen, when the macroporous adsorption resin adsorption decolorization or the anion exchange resin ion exchange decolorization is used, after the decolorization resin completes the decolorization, only the decolorization resin needs to be washed with salt water, which replaces the complex steps of flocculation, precipitation, oxidation and reduction in the prior art, and the process is simple, suitable for industrial production, and the simple decolorization process cooperates with the removal of the high-molecular and large-molecular proteins, oil tea polysaccharide, starch, large-molecular substances and small-molecular inorganic salts in the oil tea seed cake or tea seed cake extraction liquid before, further improving the purity of the oil tea saponin. After the decolorization of the dissolving solution is completed, the resin used for decolorization can be regenerated and recycled. Specifically, the resin is first washed with 1-5 wt% hydrochloric acid, then washed with water to neutral, then washed with 2-5 wt% sodium hydroxide solution, and then washed with water to neutral, and then directly used.

[0043] In some embodiments, when the decolorized solution is adsorbed by the macroporous adsorption resin, the loading speed of the decolorized solution is 1-2 BV / h, and the loading amount is 0.5-5.0 BV of the volume of the resin. When the ethanol solution is resolved, the loading speed of the ethanol solution is 0.5-1 BV / h, and the loading amount is 1.0-5.0 BV.

[0044] Specifically, the macroporous adsorption resin is a non-polar to weakly polar macroporous resin, which can be a polystyrene macroporous adsorption resin or an acrylate macroporous adsorption resin, and the particle size is 250 μm-1.25 mm and the water content is 55-75%. The type of the macroporous adsorption resin used can be one or more of AB-8, ADS-5, D101, D3520, D4006, D4020, H103, HP20, HP2MG, HPD100, HPD600, HZ801, HZ803, LX20, LX60, LK1180, LK1200, LK1300, LK1400, LK1500, LKS06, SP825, T28, T81, T83, X-5, XAD-5, XAD-8, XAD-16, and XAD-1600.

[0045] The macroporous adsorption resin adsorption is carried out on the decoloring liquid, and under the above parameter conditions, the oil tea saponin in the decoloring liquid can be effectively adsorbed, and the oil tea saponin can be extracted to a greater extent. After the macroporous adsorption resin adsorption of the decoloring liquid is completed, ethanol is used for elution. It should be understood that after the ethanol elution is completed, the macroporous adsorption resin can be continuously washed with water, and the ethanol elution liquid and the water washing liquid are collected and combined to obtain an elution liquid; after the elution and elution of the macroporous adsorption resin are completed, the macroporous adsorption resin is washed with water until no alcohol is present, and the macroporous adsorption resin can be recycled.

[0046] In some embodiments, the method for concentrating the elution liquid is as follows: the elution liquid is subjected to membrane concentration, when the solid content of the concentrated liquid reaches 20-30%, the single-effect external circulation concentrator is used for continuous concentration, and the concentration is ended when the Brix value reaches 40-50%; the specification of the membrane used in the membrane concentration is 100-200 Da; when the single-effect external circulation concentrator is used for continuous concentration, the concentration vacuum degree is 0.05-0.095 MPa, and the concentration temperature is 50-85℃.

[0047] In some embodiments, the sterilization temperature is 80-85℃, and the sterilization time is 30-35 min.

[0048] In some embodiments, the drying method is spray drying, the feed rate of the spray drying is 10-100 L / h, the inlet air temperature is 180-190℃, and the outlet air temperature is 85-90℃.

[0049] The high-purity oil tea saponin prepared by the preparation method has a purity of more than 97%, a protein content of ≤1.0 wt%, a polyphenol content of ≤1.0 g / kg, and an absorbance Abs of less than 0.06 at a wavelength of 420-610 nm. The test methods of the purity, the protein content, the polyphenol content and the absorbance of the high-purity oil tea saponin are as follows:

[0050] The test method of the purity of the high-purity oil tea saponin is GB / T41549;

[0051] The test method of the protein content of the high-purity oil tea saponin is GB5009.5;

[0052] The test method of the polyphenol content of the high-purity oil tea saponin is Folin-Ciocalteu reagent method;

[0053] The test method of the absorbance of the high-purity oil tea saponin is ultraviolet-visible spectrophotometry.

[0054] In order to better illustrate the technical solutions of the present application, the present application also provides the following specific embodiments. It should be understood that the raw materials used in the following embodiments are all commercially available raw materials unless otherwise specified.

[0055] Example 1:

[0056] A method for extracting high-purity oil tea saponin from oil tea seed cake, comprising the following steps:

[0057] (1) Raw material preparation: The oil tea seed cake is a first-class grass-free cake, and other requirements meet the GB35131 standard.

[0058] (2) Crushing and leaching: 1000 kg of raw material oil tea seed cake is crushed at a uniform feeding speed of 10 kg / h with a frequency of 30 Hz in a crusher, and the particle size of the crushed oil tea seed cake is 0.6 mm. The crushed oil tea seed cake falls into one end of a dynamic countercurrent extraction unit, and 50% concentration water-containing ethanol (containing 0.2wt% of sodium bisulfite and sodium metabisulfite, and the mass ratio of sodium bisulfite to sodium metabisulfite is 1:1) is input into the other end of the extraction unit at a flow rate of 1 m 3 / h. The extraction temperature is 50℃, the advancing speed of the screw shaft of the dynamic countercurrent extraction unit is 8 m / h, and the frequency is 30 Hz. The extraction liquid is filtered from the port pipeline filter into a temporary storage tank, and the oil tea seed cake extraction residue is pushed to the end of the unit, filtered through a grid, and dried to be used as feed.

[0059] (3) Nanofiltration membrane concentration: The filtrate is concentrated by nanofiltration membrane to recover alcohol, and the alcohol residual amount of the concentrated liquid is 1%. The membrane assembly type is hollow fiber membrane NF95, the specification is 150 Da, the temperature during nanofiltration membrane concentration is 20℃, the pressure is 0.9 MPa, the PH is 4, and the flow rate is 0.5 m 3 / h. The recovered alcohol can be recycled after rectification.

[0060] (4) Dilution: The concentrated liquid is diluted with water, and the Brix value of the diluted liquid is 6%.

[0061] (5) Ultrafiltration membrane ultrafiltration and nanofiltration membrane concentration: The diluted liquid is ultrafiltered by an ultrafiltration membrane, the membrane assembly type is NF01, the membrane specification is 15 KDa, the inlet membrane pressure is maintained at 0.3 MPa during operation, the temperature is 25℃, the PH is 3, and the flow rate is 0.5 m 3 / h. At the same time, water is continuously added for dialysis, macromolecular substances with a molecular weight greater than 20 KDa are intercepted, and the Brix value of the permeate is 0.2%. The permeate is concentrated by a series of nanofiltration membranes, the nanofiltration membrane is NF10, the specification is 400 Da, and substances with a molecular weight less than 400 Da can pass through, and substances with a molecular weight greater than 600 Da are intercepted. The operating pressure is 0.8 MPa, the temperature is 10℃, the pH is 3, the flow rate of the ultrafiltration membrane permeate is 1.6 m3 / h, and the Brix value of the concentrated liquid is 25%.

[0062] (6) Resin column decolorization: the concentrated solution obtained in step (5) is dissolved in deionized water, the Brix value of the dissolved solution is 8%, the dissolved solution is subjected to decolorization on a resin column LX600J, the feeding speed is 1 BV / h, the feeding amount is 5 BV of the resin volume, the front effluent water is discarded, the effluent solution is collected when the feed solution flows out, after the feeding is completed, the residual solution is eluted with 2.5 times the resin volume of 2wt% salt water, the effluent solution and the water elution are collected together to obtain a decolorized solution.

[0063] (7) Macroporous resin adsorption: the decolorized solution is fed into a macroporous adsorption resin HP20 for adsorption, the feeding speed is 1 BV / h, the feeding amount is 5 BV of the resin volume, after the feeding is completed, the residual solution is washed with 2-3 BV of the resin volume of water, the effluent solution and the washing solution are discarded, 2 BV of the resin volume of 85% ethanol is used for elution and resolution, the elution speed is 0.8 BV / h, then 2 times the resin volume of water is used to elute the alcohol, and the elution solution and the water elution are combined to obtain a resolution solution.

[0064] (8) Concentration: the resolution solution is subjected to membrane concentration, the membrane assembly type is hollow fiber membrane NF95, the specification is 200Da, ethanol is recovered to be free of alcohol, when the Brix value of the concentrated solution is 22%, the concentrated solution is transferred to a single-effect external circulation concentrator for further concentration, the concentration vacuum degree is 0.05 MPa, the concentration temperature is 60°C, and the concentration is ended when the Brix value of the concentrated solution is 40%.

[0065] (9) Sterilization: the concentrated solution is subjected to pasteurization, and is kept at 82°C for 35 min.

[0066] (10) Drying: the concentrated solution after sterilization is filtered through a pipeline filter and then is subjected to spray drying, the feeding rate is adjusted to be 100 L / h, the air inlet temperature is 190°C, and the air outlet temperature is 85°C. The product is collected, the yield of the high-purity oil tea saponin product is 10.4%, the extraction rate is 78.8%, and the oil tea saponin content is 98.5%. The purity, the protein content, the polyphenol content and the absorbance of the high-purity oil tea saponin product are detected respectively, and the results are shown in Table 1.

[0067] Example 2

[0068] A method for extracting high-purity oil tea saponin from oil tea seed cake, comprising the following steps:

[0069] (1) Raw material preparation: the oil tea seed cake is first-class grass-free cake, and other requirements meet the GB35131 standard, and is commercially available.

[0070] (2) Pulverization and leaching: 1000 kg of raw oil tea seed cake is weighed, the scraper is uniformly fed at a speed of 160 kg / h, and the frequency is adjusted to 45 Hz. After being pulverized in the pulverizer, the oil tea seed meal particles have a particle size of 0.1 mm, fall into one end of the dynamic countercurrent extraction machine set, and the other end is input through a pipeline with a concentration of 70% methanol containing 0.4wt% sodium bisulfite and sodium sulfite (the mass ratio of sodium bisulfite to sodium sulfite is 1:1) containing water (ethanol containing water), and extraction is carried out at a flow rate of 1 m 3 / h. The extraction temperature is 38°C, the advancing speed of the spiral shaft of the dynamic countercurrent extraction machine set is 8.5 m / h, and the frequency is 42 Hz. The extraction liquid is filtered from the port pipeline filter to the temporary storage tank, and the oil tea seed meal extraction residue is pushed to the end of the machine set, filtered through a grid, dried, and used as feed.

[0071] (3) Nanofiltration membrane concentration: the filtrate is concentrated by nanofiltration membrane to recover alcohol, and the alcohol residual amount of the concentrated liquid is 1.5%. The membrane module type is hollow fiber membrane NF95, the specification is 165 Da, the temperature during nanofiltration membrane concentration is 35°C, the pressure is 1.5 MPa, the PH is 3, and the flow rate is 1.6 m 3 / h. The recovered alcohol can be recycled after rectification.

[0072] (4) Dilution: the concentrated liquid is diluted with water, and the Brix value of the diluted liquid is 1%.

[0073] (5) Ultrafiltration membrane ultrafiltration and nanofiltration membrane concentration: the diluted liquid is ultrafiltered by an ultrafiltration membrane, the membrane module type is NF01, the membrane specification is 18 KDa, the inlet membrane pressure is maintained at 0.1 MPa during operation, the temperature is 37°C, the PH is 5, and the flow rate is 1.6 m 3 / h, while constantly adding water for dialysis, the molecular weight of the macromolecular substances to be intercepted is greater than 20 KDa, until the Brix value of the permeate is 0.35%, and the permeate is collected. The permeate is concentrated by a series of nanofiltration membranes, the nanofiltration membrane is NF10, the specification is 460 Da, and the substances with a molecular weight less than 400 Da can be permeated, and the substances with a molecular weight greater than 600 Da are intercepted. The operating pressure is 1.5 MPa, the temperature is 37°C, the pH is 8, the flow rate of the ultrafiltration membrane permeate is 3 m3 / h, and the Brix value of the concentrated liquid is 28% after concentration.

[0074] (6) Resin column decolorization: the concentrated liquid obtained in step (5) is dissolved in deionized water, the Brix value of the dissolved liquid is 9%, the dissolved liquid is subjected to decolorization on a resin column D941, the sampling speed is 0.65 BV / h, the sampling amount is 3.8 BV of the resin volume, the front effluent is discarded, the sample liquid begins to be collected, and after the sampling is completed, 2.5 times the volume of the resin is used to elute the residual liquid with 2wt% salt water, and the effluent and the water eluent are collected together to obtain the decolorized liquid.

[0075] (7) Macroporous resin adsorption: the decolorizing liquid is fed into macroporous adsorption resin LK20, the feeding speed is 1.5 BV / h, the feeding amount is 0.5 BV of the volume of the resin, after the feeding is completed, the residual liquid is washed away with 2-3 BV of water, the effluent and the washing liquid are discarded, 85% ethanol is used to elute and resolve 3.8 BV of the volume of the resin, the elution speed is 0.5 BV / h, then 2 times of the volume of water is used to top the alcohol, and the elution liquid and the water top liquid are combined as the resolution liquid.

[0076] (8) Concentration: the resolution liquid is concentrated by a membrane, the type of the membrane assembly is hollow fiber membrane NF95, the specification is 180 Da, ethanol is recovered until there is no ethanol, when the Brix value of the concentrated liquid is 20%, the concentrated liquid is transferred into a single-effect external circulation concentrator for further concentration, the concentration vacuum degree is 0.08 MPa, the concentration temperature is 50℃, and the concentration is ended until the Brix value of the concentrated liquid is 45%.

[0077] (9) Sterilization: the concentrated liquid is subjected to pasteurization, and is kept at 84℃ for 32 min.

[0078] (10) Drying: the concentrated liquid after sterilization is filtered by a pipeline filter, and then is subjected to spray drying, the feeding rate is adjusted to 10 L / h, the air inlet temperature is 180℃, and the air outlet temperature is 87℃. The product is collected, the yield of the high-purity tea saponin in the final product is 10.9%, the extraction rate is 82.6%, and the content of the tea saponin is 98.7%. The purity, the protein content, the polyphenol content and the absorbance of the high-purity tea saponin product are detected respectively, and the results are shown in Table 1.

[0079] Example 3

[0080] A method for extracting high-purity tea saponin from oil tea seed cake, comprising the following steps:

[0081] (1) Raw material preparation: the oil tea seed cake is first-class grass-free cake, and other requirements meet the GB35131 standard, and is commercially available.

[0082] (2) Crushing and extraction: 1000 kg of the raw material oil tea seed cake is weighed, the scraper is uniformly fed at a speed of 50 kg / h, the frequency is adjusted to 50 Hz, the oil tea seed cake is crushed in the crusher to a particle size of 1.0 mm, and then is dropped into one end of a dynamic countercurrent extraction machine set, and 75% methanol containing water (0.1wt% of sodium sulfite, sodium bisulfite and sodium metabisulfite, and the mass ratio of sodium sulfite, sodium bisulfite and sodium metabisulfite is 1:2:3) is input into the other end of the extraction machine set at a flow rate of 1 m 3 / h for extraction. The extraction temperature is 33℃, the advancing speed of the spiral shaft of the dynamic countercurrent extraction machine set is 9 m / h, and the frequency is 50 Hz. The extraction liquid is filtered out from the port pipeline filter into a temporary storage tank, and the oil tea seed cake extraction residue is pushed to the end of the machine set, filtered through a grid, and dried to be used as feed.

[0083] (3) Nanofiltration membrane concentration: the filtrate is subjected to nanofiltration membrane concentration to recover alcohol, and the alcohol residual amount of the concentrated solution is 2.8%. The membrane module type is hollow fiber membrane NF95, the specification is 190Da, the temperature during nanofiltration membrane concentration is 10°C, the pressure is 0.5MPa, the PH is 9, and the flow rate is 2.5m 3 / h. The recovered alcohol can be recycled after being rectified.

[0084] (4) Dilution: the concentrated solution is diluted with water, and the Brix value of the diluted solution is 8%.

[0085] (5) Ultrafiltration membrane ultrafiltration and nanofiltration membrane concentration: the diluted solution is subjected to ultrafiltration membrane ultrafiltration, the membrane module type is NF01, the membrane specification is 17KDa, the inlet membrane pressure is maintained at 1MPa during operation, the temperature is 65°C, the PH is 7, and the flow rate is 3.0m 3 / h, and water is continuously added for dialysis at the same time, macromolecular substances with a molecular weight greater than 20KDa are intercepted, until the Brix value of the permeate is 0.5%, and the permeate is collected. The permeate is subjected to nanofiltration membrane concentration in series, the nanofiltration membrane is NF10, the specification is 550Da, and substances with a molecular weight less than 400Da and greater than 600Da can be permeated. The pressure during operation is 2.0MPa, the temperature is 50°C, the pH is 6, the flow rate of the ultrafiltration membrane permeate is 3.8m3 / h, and the concentration is performed until the Brix value of the concentrated solution is 30%.

[0086] (6) Resin column decolorization: the concentrated solution obtained in step (5) is dissolved in deionized water, the Brix value of the dissolved solution is 9.5%, the dissolved solution is subjected to decolorization on a resin column D900, the sampling speed is 0.7BV / h, the sampling amount is 2.5BV of the resin volume, the front effluent is discarded, the sample liquid begins to be collected, after the sampling is completed, 2.5 times the resin volume of 2wt% salt water is used to elute the residual liquid, and the effluent and the water elution are collected together to obtain a decolorized solution.

[0087] (7) Macroporous resin adsorption: the decolorized solution is subjected to macroporous adsorption on a macroporous resin AB-8, the sampling speed is 1.8BV / h, the sampling amount is 4.2BV of the resin volume, after the sampling is completed, the residual liquid is washed with 2-3BV of the resin volume of water, the effluent and the washing liquid are discarded, 4.5BV of the resin volume of 85% ethanol is used for elution and resolution, the elution speed is 0.7BV / h, then 2 times the resin volume of water is used to elute the alcohol, and the elution liquid and the water elution are combined to obtain a resolution liquid.

[0088] (8) Concentration: the resolution liquid is subjected to membrane concentration, the membrane module type is hollow fiber membrane NF95, the specification is 160Da, the ethanol is recovered to be alcohol-free, when the Brix value of the concentrated solution is 26%, the concentrated solution is transferred to a single-effect external circulation concentrator for further concentration, the concentration vacuum degree is 0.06MPa, the concentration temperature is 75°C, and the concentration is ended until the Brix value of the concentrated solution is 48%.

[0089] (9) Sterilization: Pasteurize the concentrate and keep it at 80°C for 30 minutes.

[0090] (10) Drying: The sterilized concentrate was filtered through a pipeline filter and then spray-dried. The feed rate was adjusted to 25 L / h, the inlet air temperature was 185℃, and the outlet air temperature was 88℃. The product was collected, and the final product had a high-purity camellia saponin yield of 11.1%, an extraction rate of 85.1%, and a camellia saponin content of 99.3%. The purity, protein content, polyphenol content, and absorbance of the high-purity camellia saponin product were tested, and the results are shown in Table 1.

[0091] Example 4

[0092] A method for extracting high-purity camellia saponins from camellia seed cake includes the following steps:

[0093] (1) Raw material preparation: Camellia seed cake is grade 1 grass-free cake, and other aspects meet the requirements of GB35131 standard and are commercially available.

[0094] (2) Crushing and Extraction: Weigh 1000 kg of raw camellia seed cake, feed it evenly with a scraper at a speed of 100 kg / h, and adjust the frequency to 40 Hz. After crushing in the crusher, the camellia seed cake particles have a particle size of 2.0 mm and fall into one end of the dynamic countercurrent extraction unit. The other end of the extraction unit is fed with 75% aqueous methanol (containing 0.3 wt% sodium metabisulfite) through a pipeline at a flow rate of 1 m / s. 3 Extraction is carried out at a rate of 10 m / h. The extraction temperature is 45℃, the propulsion speed of the spiral shaft of the dynamic countercurrent extraction unit is 10 m / h, and the frequency is 35 Hz. The extract flows from the port pipeline filter into a temporary storage tank. The camellia seed meal extraction residue is pushed to the end of the unit, filtered by a grid, and dried before being used as animal feed.

[0095] (3) Nanofiltration membrane concentration: The filtrate is concentrated using a nanofiltration membrane to recover alcohol until the residual alcohol content in the concentrate is 0.5%. The membrane module is a hollow fiber membrane NF95, 200 Da. The concentration temperature is 50℃, the pressure is 2.5 MPa, the pH is 5, and the flow rate is 3.8 m / s². 3 / h, the recovered alcohol can be purified and recycled.

[0096] (4) Dilution: Dilute the concentrate with water to a Brix value of 3%.

[0097] (5) Ultrafiltration and Nanofiltration Concentration: The diluted solution was ultrafiltered through an ultrafiltration membrane (NF01, 19 kDa). During operation, the inlet membrane pressure was maintained at 0.5 MPa, the temperature at 50°C, the pH at 9, and the flow rate at 3.8 m / s². 3The concentrated solution obtained in step (5) is dissolved in deionized water, and the Brix value of the solution is 8.3%. The solution is fed to a resin column SD331 for decolorization at a feeding speed of 0.9 BV / h and a feeding amount of 0.9 BV of the resin volume. The front effluent is discarded, and the effluent is collected. After the feeding is completed, the residual solution is eluted with 2.5 times the resin volume of 2 wt% salt water. The effluent and the water eluent are collected together to obtain a decolorized solution.

[0098] (6) Resin column decolorization: the concentrated solution obtained in step (5) is dissolved in deionized water, and the Brix value of the solution is 8.3%. The solution is fed to a resin column SD331 for decolorization at a feeding speed of 0.9 BV / h and a feeding amount of 0.9 BV of the resin volume. The front effluent is discarded, and the effluent is collected. After the feeding is completed, the residual solution is eluted with 2.5 times the resin volume of 2 wt% salt water. The effluent and the water eluent are collected together to obtain a decolorized solution.

[0099] (7) Macroporous resin adsorption: the decolorized solution is fed to a macroporous adsorption resin LX60 for adsorption at a feeding speed of 1.5 BV / h and a feeding amount of 2.8 BV of the resin volume. After the feeding is completed, the residual solution is washed with 2-3 BV of the resin volume of water, and the effluent and the washing liquid are discarded. Then, 5 BV of the resin volume of 85% ethanol is used for elution and resolution at a speed of 0.9 BV / h. Then, 2 times the resin volume of water is used to elute the alcohol, and the eluent and the water eluent are collected together to obtain a resolution solution.

[0100] (8) Concentration: the resolution solution is concentrated by a membrane assembly, and the type of the membrane is a hollow fiber membrane NF95 with a specification of 100 Da. Ethanol is recovered until there is no ethanol. When the Brix value of the concentrated solution is 30%, the concentrated solution is transferred to a single-effect external circulation concentrator for further concentration. The concentration vacuum degree is 0.075 MPa, and the concentration temperature is 85°C. The concentration is ended when the Brix value of the concentrated solution is 50%.

[0101] (9) Sterilization: the concentrated solution is subjected to pasteurization at 83°C for 31 min.

[0102] (10) Drying: the concentrated solution after sterilization is filtered by a pipeline filter and then subjected to spray drying. The feeding rate is adjusted to 75 L / h, the air inlet temperature is 186°C, and the air outlet temperature is 90°C. The product is collected. The yield of the high-purity oil tea saponin product is 10.9%, the extraction rate is 83.5%, and the content of the oil tea saponin is 98.8%. The purity, the protein content, the polyphenol content, and the absorbance of the high-purity oil tea saponin product are detected, and the results are shown in Table 1.

[0103] Example 5

[0104] A method for extracting high-purity oil tea saponin from oil tea seed cake, comprising the following steps:

[0105] (1) Raw material preparation: camellia seed cake is a first-class grass-free cake, and other requirements meet the GB35131 standard requirements, and is commercially available.

[0106] (2) Grinding and extraction: 1000 kg of raw material camellia seed cake is weighed, the scraper is uniformly fed at a feeding speed of 200 kg / h, and the frequency is adjusted to 45 Hz. After grinding in the grinder, the particle size of the camellia seed meal is 1.6 mm, which falls into one end of the dynamic countercurrent extraction unit. The other end of the extraction unit is input through the pipeline with a concentration of 90% water-containing ethanol (containing 0.5wt% sodium sulfite) at a flow rate of 1 m 3 / h. The extraction temperature is 30℃, the advancing speed of the spiral shaft of the dynamic countercurrent extraction unit is 5 m / h, and the frequency is 40 Hz. The extraction liquid is filtered from the port pipeline filter to the temporary storage tank, and the camellia seed cake extraction residue is pushed to the end of the unit after being filtered and dried through the grid, which can be used as feed.

[0107] (3) Nanofiltration membrane concentration: the filtrate is concentrated by nanofiltration membrane to recover alcohol, and the alcohol residual amount of the concentrated liquid is 2%. The membrane module type is hollow fiber membrane NF95, the specification is 185 Da, the temperature during nanofiltration membrane concentration is 65℃, the pressure is 3 MPa, the PH is 12, and the flow rate is 5 m 3 / h. The recovered alcohol can be rectified and recycled.

[0108] (4) Dilution: the concentrated liquid is diluted with water, and the Brix value of the dilution liquid is 10%.

[0109] (5) Ultrafiltration membrane ultrafiltration and nanofiltration membrane concentration: the dilution liquid is ultrafiltered by an ultrafiltration membrane, the membrane module type is NF01, the membrane specification is 20KDa, the inlet membrane pressure is maintained at 0.8 MPa during operation, the temperature is 10℃, the PH is 12, and the flow rate is 5 m 3 / h. At the same time, water is constantly dialyzed, macromolecular substances with a molecular weight greater than 20KDa are intercepted, until the Brix value of the permeate is 0.4%, and the permeate is collected. The permeate is concentrated by a series of nanofiltration membranes, the nanofiltration membrane NF10 has a specification of 600 Da, can pass substances with a molecular weight less than 400 Da, and intercept substances with a molecular weight greater than 600 Da. The operating pressure is 0.1 MPa, the temperature is 25℃, the pH is 10, the flow rate of the ultrafiltration membrane permeate is 5 m3 / h, and the Brix value of the concentrated liquid is 27.5% after concentration.

[0110] (6) Resin column decolorization: the concentrated solution obtained in step (5) was dissolved in deionized water, the Brix value of the solution was 10%, and the solution was subjected to decolorization by a mixed resin of LX600J and DM100, the feeding speed was 0.5 BV / h, the feeding amount was 0.5 BV of the volume of the resin, the front effluent water was discarded, the effluent liquid was collected when the feed liquid began to flow, and the residual liquid was eluted by 2.5 times the volume of the resin with 2 wt% salt water after the feeding was completed, and the effluent liquid and the water elution were collected together to obtain a decolorized liquid.

[0111] (7) Macroporous resin adsorption: the decolorized liquid was fed into a macroporous adsorption resin AB-8 for adsorption, the feeding speed was 2 BV / h, the feeding amount was 1.6 BV of the volume of the resin, and after the feeding was completed, the residual liquid was washed with 2-3 BV of water, the effluent liquid and the washing liquid were discarded, 85% ethanol was used to elute and resolve 1 BV of the volume of the resin, the elution speed was 1 BV / h, then 2 times the volume of the resin was used to elute the alcohol with water, and the elution liquid and the water elution were collected together to obtain a resolved liquid.

[0112] (8) Concentration: the resolved liquid was subjected to membrane concentration, the membrane assembly type was hollow fiber membrane NF95, the specification was 130 Da, ethanol was recovered to be free of alcohol, and when the Brix value of the concentrated solution was 25%, the concentrated solution was transferred to a single-effect external circulation concentrator for further concentration, the concentration vacuum degree was 0.095 MPa, the concentration temperature was 58°C, and the concentration was ended when the Brix value of the concentrated solution was 43%.

[0113] (9) Sterilization: the concentrated solution was subjected to pasteurization, and the sterilization was performed at 85°C for 35 min.

[0114] (10) Drying: the concentrated solution after sterilization was filtered by a pipeline filter and then subjected to spray drying, the feeding rate was adjusted to be 50 L / h, the air inlet temperature was 182°C, and the air outlet temperature was 86°C. The product was collected, the yield of the high-purity oil tea saponin product was 10.8%, the extraction rate was 81.7%, and the oil tea saponin content was 97.9%. The purity, protein content, polyphenol content and absorbance of the high-purity oil tea saponin product were detected respectively, and the results are shown in Table 1.

[0115] Example 6

[0116] The high-purity oil tea saponin was extracted according to the method of Example 5, and the difference from Example 5 was that sodium sulfite, sodium bisulfite and sodium metabisulfite were contained in the aqueous ethanol used in step (2), and the mass ratio of sodium sulfite, sodium bisulfite and sodium metabisulfite was 2:1:2.

[0117] The yield of the high-purity oil tea saponin product was 11.3%, the extraction rate was 86.9%, and the oil tea saponin content was 99.7%. The purity, protein content, polyphenol content and absorbance of the high-purity oil tea saponin product were detected respectively, and the results are shown in Table 1.

[0118] Comparative Example 1

[0119] The high-purity camellia saponin was extracted by the method of Example 3, with the only difference being that the aqueous ethanol used in step (2) did not contain sodium sulfite, sodium bisulfite and sodium metabisulfite.

[0120] The yield of the high-purity camellia saponin product was 10.2%, the extraction rate was 72.4%, and the camellia saponin content was 91.6%. The purity, protein content, polyphenol content and absorbance of the high-purity camellia saponin product were detected, and the results are shown in Table 1.

[0121] Comparative Example 2

[0122] The high-purity camellia saponin was extracted by the method of Example 3, with the only difference being that the aqueous ethanol used in step (2) did not contain sodium sulfite, sodium bisulfite and sodium metabisulfite, and the dilution liquid of step (4) was directly subjected to macroporous resin adsorption of step (7) without the treatment of steps (5)-(6).

[0123] The yield of the high-purity camellia saponin product was 9.5%, the extraction rate was 60.9%, and the camellia saponin content was 83.2%. The purity, protein content, polyphenol content and absorbance of the high-purity camellia saponin product were detected, and the results are shown in Table 1.

[0124] Table 1 Performance parameters of camellia saponin products prepared in examples and comparative examples

[0125]

[0126] It should be noted that for the detection of polyphenol content, when the polyphenol content is less than 0.05 g / kg, it cannot be detected, so "not detected" in Table 1 means that the polyphenol content is less than 0.05 g / kg.

[0127] From the examples 1-5, it can be seen that the extraction rate of the camellia saponin is more than 80% by using the method of the present application to extract the camellia saponin from the oil tea seed cake, and the purity of the camellia saponin product is more than 97%. From the comparison between the example 5 and the example 6, it can be seen that in the water low alcohol solution used for the extraction of the oil tea seed cake, the purity of the camellia saponin prepared is higher, the protein and polyphenol content of the camellia saponin is lower, and the absorbance is lower when the water low alcohol solution contains the complex salt than when the water low alcohol solution contains only the single salt. From the comparison between the example 3 and the comparative example 1, it can be seen that in the water low alcohol solution used for the extraction of the oil tea seed cake, the purity of the camellia saponin prepared is higher, the protein and polyphenol content of the camellia saponin is lower, and the absorbance is lower when the water low alcohol solution contains the complex salt than when the water low alcohol solution does not contain the complex salt. From the comparison between the example 3 and the comparative example 2, it can be seen that in the water low alcohol solution containing the complex salt used for the extraction of the oil tea seed cake, the purity of the camellia saponin prepared is higher, the protein and polyphenol content of the camellia saponin is lower, and the absorbance is lower when the water low alcohol solution is used for the extraction of the oil tea seed cake and the operation of the steps (5)-(6) of the example 3 is performed under the synergistic effect of the above conditions.

[0128] The above only provides the preferred embodiments of the present application and is not used to limit the present application. Although the present application is described in detail with reference to the foregoing embodiments, those skilled in the art can modify the technical solutions recorded in the foregoing embodiments or equivalently replace some technical features. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for extracting high-purity camellia saponins, characterized in that, Includes the following steps: The camellia seed cake or tea seed cake is crushed, and the crushed camellia seed cake or tea seed cake is dynamically countercurrently extracted with an aqueous low alcohol solution, and the filtrate is collected. The filtrate is concentrated to recover alcohol until the alcohol content in the concentrate is less than 3 wt%, thus obtaining concentrate A; The concentrate A is diluted with water, the diluted solution is treated with an ultrafiltration membrane, and the permeate from the ultrafiltration membrane is concentrated with a nanofiltration membrane to obtain concentrate B. Water is added to the concentrated solution B to obtain a solution. The solution is then decolorized, and the decolorized solution is adsorbed by a macroporous adsorption resin and then eluted with an ethanol solution to obtain an eluent. The eluent was concentrated, sterilized, filtered, and dried to obtain high-purity camellia saponins. The aqueous lower alcohol solution comprises a lower alcohol, a compound salt, and water, wherein the mass concentration of the lower alcohol is 50-90% and the mass concentration of the compound salt is 0.1-0.5%; the compound salt comprises sulfite, bisulfite, and metabisulfite; wherein the mass ratio of sulfite, bisulfite, and metabisulfite is (1-2):(1-2):(2-3).

2. The extraction method according to claim 1, characterized in that, The conditions for pulverizing the camellia seed cake or tea seed cake are: a feeding speed of 10-200 kg / h and a frequency of 30-50 Hz; the particle size of the pulverized camellia seed cake or tea seed cake is 0.1-2 mm; and / or, When performing dynamic countercurrent extraction on the crushed camellia seed cake or tea seed cake, the extraction temperature is 30-50℃, the extraction frequency is 30-50HZ, and the extraction propulsion speed is 5-10m / h.

3. The extraction method according to claim 1, characterized in that, The method for concentrating and recovering alcohol from the filtrate is nanofiltration membrane concentration, wherein the nanofiltration membrane has a specification of 150-200 Da, the operating pressure of the nanofiltration membrane is 0.5-3.0 MPa, the temperature is 10-65℃, the pH is 3.0-12.0, and the flow rate of the filtrate is 0.5-5.0 m³ / h.

4. The extraction method according to claim 1, characterized in that, The Brix value of the diluted solution after dilution with water of the concentrate A is 1-10%; and / or, When the diluent is treated by an ultrafiltration membrane, the ultrafiltration membrane has a specification of 15-20 kDa, the inlet pressure is 0.1-1.0 MPa, the temperature is 10-65℃, the pH is 3.0-12.0, the flow rate of the diluent is 0.5-5.0 m³ / h, and large molecules with a molecular weight greater than 20 kDa are retained. Water is continuously added for dialysis until the Brix value of the permeate is ≤0.5%.

5. The extraction method according to claim 1, characterized in that, When the permeate from the ultrafiltration membrane is concentrated by the nanofiltration membrane, the nanofiltration membrane has a specification of 400-600 Da, the operating pressure is 0.1-3.0 MPa, the temperature is 10-65℃, the pH is 3.0-12.0, and the flow rate of the permeate from the ultrafiltration membrane is 0.5-5.0 m³ / h, until the Brix value of the concentrate is 25-30%, thus obtaining concentrate B.

6. The extraction method according to claim 1, characterized in that, The Brix value of the solution is 8-10%; and / or, The decolorization method of the solution involves adsorption by a macroporous adsorption resin or ion exchange by an anion exchange resin. During decolorization, the loading rate of the solution is 0.5-1 BV / h, and the loading volume is 0.5-5.0 BV of the resin volume. After decolorization by the macroporous adsorption resin or anion exchange resin, a decolorized solution is obtained, and / or... The macroporous adsorption resin is a polystyrene macroporous adsorption resin or an acrylate macroporous adsorption resin, and the anion exchange resin is a polystyrene skeleton or an acrylate skeleton anion exchange resin.

7. The extraction method according to claim 6, characterized in that, When the decolorizing solution is adsorbed by the macroporous adsorption resin, the loading rate of the decolorizing solution is 1-2 BV / h, and the loading amount is 0.5-5.0 BV of the resin volume.

8. The extraction method according to claim 1, characterized in that, During the ethanol solution analysis, the ethanol solution loading rate is 0.5-1 BV / h, and the loading volume is 1.0-5.0 BV of the resin volume.

9. The extraction method according to claim 1, characterized in that, The method for concentrating the eluent is as follows: the eluent is concentrated using a membrane; when the solid content of the concentrate reaches 20-30%, it is transferred to a single-effect external circulation concentrator for further concentration until the Brix value reaches 40-50%; the membrane used for membrane concentration has a specification of 100-200 Da; during the further concentration in the single-effect external circulation concentrator, the concentration vacuum degree is 0.05-0.095 MPa, and the concentration temperature is 50-85℃; and / or, The sterilization temperature is 80-85℃, and the sterilization time is 30-35 minutes; and / or, The drying method is spray drying, wherein the feed rate of the spray drying is 10-100 L / h, the inlet air temperature is 180-190℃, and the outlet air temperature is 85-90℃.

Images