CN113546574B

CN113546574B - High-stability saponin composition and application thereof

Info

Publication number: CN113546574B
Application number: CN202110698266.8A
Authority: CN
Inventors: 王孔江; 辛亮; 王颖; 毛勇进
Original assignee: Guangdong Jingcui Biotechnology Co ltd; Institute of Biophysics of CAS
Current assignee: Guangdong Jingcui Biotechnology Co ltd
Priority date: 2021-06-23
Filing date: 2021-06-23
Publication date: 2022-04-12
Anticipated expiration: 2041-06-23
Also published as: CN113546574A; WO2022268235A1

Abstract

The invention relates to the technical field of plant extraction, and particularly relates to a saponin composition with high stability and a preparation method thereof. The saponin composition is extracted from natural plants; the specific extraction steps comprise: s1, pretreating a natural plant; s2, extracting the pretreated natural plant to obtain an extracting solution; s3, clarifying the extracting solution to obtain a clarified solution; s4, decolorizing the clarified liquid to obtain a decolorized liquid; and S5, refining the decolorized solution to obtain a finished product. The saponin composition obtained by the invention has the following advantages: (1) the invention adopts the green and environment-friendly extraction method to efficiently extract the saponin composition from the plant raw materials, and the method has the advantages of low cost, simple and convenient process and strong feasibility, and is suitable for the field of natural surfactants; (2) the saponin composition prepared by the invention has high purity and strong color stability; (3) the saponin composition prepared by the invention has excellent comprehensive performance, low irritation and high decontamination capability, and the heavy metal content meets the industrial specification.

Description

High-stability saponin composition and application thereof

Technical Field

The invention relates to the technical field of plant extraction, and particularly relates to a saponin composition with high stability and application thereof.

Background

The surfactant is an oil-water amphiphilic substance with the effect of reducing the surface energy of the reagent, and is a large amount of core raw materials of daily chemical industry. Worldwide surfactant production of 2120 million tons in 2015; 2025, world surfactant market is expected to produce values as high as seven billion dollars, with broad market prospects. The surfactants in the current market can be divided into two categories, namely synthetic surfactants and green surfactants according to raw materials, the synthetic surfactants are mostly from petrochemical industry, the raw materials are organic reagents such as alkylbenzene, ethylene oxide and the like, water and soil pollution is easily caused, and the surfactants have strong irritation to skin and potential health hazards to the environment and human bodies. The green surfactant is a surfactant produced by chemical synthesis from natural oil and plant carbohydrate, and compared with a synthetic surfactant, the green surfactant has the advantages of low irritation and strong degradability, but still has the problems of chemical residue risk, high cost and the like.

The production technology of pure natural non-synthetic surfactants is not mature, and the natural surfactants can be used for daily chemical products in a few choices, and saponin is just one of the natural surfactants. As a representative of natural surfactants, saponins have incomparable advantages over chemically synthesized surfactants: firstly, the biological degradability is good, the biological degradable soap can be degraded by 100% quickly in natural environment, secondly, the irritation to human skin is low, the property is mild, most importantly, the decontamination capability of saponin is superior to that of sodium alkyl benzene sulfonate and other substances, and the saponin has the potential of gradually replacing chemical synthetic surfactants. The saponin is a compound formed by condensing sugar and sapogenin, exists in a natural plant in a mixture form, is used as a main secondary metabolite of plants of camellia, soapberry and gleditsia, has very high saponin content in plants such as soapberry pericarp, tea seed cake and gleditsia sinensis, and is oleanane type triterpenoid saponin; before the rise of the modern chemical industry, soapberry fruit peel, tea seed cake and soap pod are used for daily washing for a long time.

At present, the scale of the sapindus mukorossi peels planted in Guangdong, Fujian, Hunan, Jiangxi, Guizhou, Sichuan and other places in China exceeds 100 ten thousand mu. The main application of the soapberry kernel is oil pressing, and the soapberry oil is used for preparing industrial diesel. Due to the long-term low international oil prices, the benefits of forest farmers who plant soapberry trees are quite limited. 56% of the dry weight of the soapberry fruit is the pericarp, which has a saponin content of about 30%. However, the technology for industrially extracting the sapindus saponin is still lacked, which is a bottleneck for restricting the development of the sapindus. The existing saponin extraction technology has many defects, and can not be industrially produced in a large scale, and can not be applied to daily chemical products in a large scale. The defects in the prior art mainly comprise the following points: 1. color depth: the traditional soapberry extraction method comprises the steps of crushing raw materials, adding ethanol or n-butanol, and extracting to obtain a product which is dark brown; while the antioxidant is added in the extraction process, the color of the soapberry extract can be prevented from being darkened, and the color of the final product is also reddish brown because the color of the soapberry extract is dark reddish brown; 2. poor stability: the existing saponin extracting solution has low purity, contains components such as protein, polyphenol, pectin and the like, and the components can interact with each other, and can generate precipitate or irreversibly darken in color after being stored for a short time, so that the extracting solution is difficult to store for a long time; 3. the cost is high: the existing saponin extraction process usually uses organic solvents to extract saponin, and the common solvents comprise ethanol, methanol, n-butanol and the like; after the first extraction step of extracting the saponin by using the organic solvent, the purity of the saponin is higher than that of water extraction, but the cost of the solvent and the price of raw materials cause that the production cost of the saponin is high, and the saponin is difficult to be put into batch industrial production.

In conclusion, no technical scheme capable of solving the problems of color, purity, cost and the like at the same time exists in the prior art, so that pure natural plant surfactant products in daily chemical products in the market at present have dark brown color and poor stability; or only adding small amount of fructus Sapindi Mukouossi or fructus Camelliae sinensis dry extract, and main surfactant or chemical synthetic surfactant. Under such a background, the present invention provides a green and environment-friendly extraction process for extracting saponin from plant material, which can solve all the above problems. The saponin composition provided by the invention has the advantages of light color, high purity and strong stability, and can be widely applied to daily chemical products.

Disclosure of Invention

The saponin composition with high stability provided by the invention solves the problem that the cost, purity and stability of the existing natural surfactant are difficult to be considered simultaneously, and realizes the saponin composition with low cost, high efficiency and excellent product performance.

In a first aspect, the present invention provides a saponin composition, which is extracted from a natural plant; the specific extraction steps comprise:

s1, pretreating a natural plant;

s2, extracting the pretreated natural plant to obtain an extracting solution;

s3, clarifying the extracting solution to obtain a clarified solution;

s4, decolorizing the clarified liquid to obtain a decolorized liquid;

and S5, refining the decolorized solution to obtain a finished product.

In a preferred embodiment, the natural plant comprises at least one of soapberry, camellia japonica, gleditsia sinensis, soapwort, quillaja saponaria, polygala tenuifolia, turmeric, ginseng, platycodon grandiflorum, bupleurum, anemarrhena asphodeloides bunge and liquorice.

In a preferred embodiment, the pretreatment step is specifically to pulverize the natural plant to 3-100 mesh to obtain natural plant powder.

In a preferred embodiment, the extraction step is specifically that natural plant powder is dissolved in an extracting agent, stirred and filtered to obtain an extracting solution; the weight ratio of the natural plant powder to the extractant is 1: (1.5-4).

In a preferred embodiment, the extractant comprises at least one of water, filter residue secondary filtrate, methanol, ethanol, acetone, n-butanol and ethyl acetate.

In a preferred embodiment, the secondary filter liquid of the filter residue is specifically prepared by dissolving natural plant powder in water, stirring at 45-65 ℃, performing solid-liquid separation, collecting the filter residue, re-dissolving in water, stirring at 45-65 ℃, performing solid-liquid separation again, and obtaining the liquid, namely the secondary filter liquid of the filter residue.

In a preferred embodiment, the clarification step is specifically to add a flocculating agent and a microporous material into the extracting solution in sequence, stir the mixture evenly, and separate solid impurities to obtain a clarified solution; the weight ratio of the extracting solution, the flocculating agent and the microporous material is 1500-: 1-2: 40-230.

In a preferred embodiment, the microporous material comprises at least one of diatomaceous earth, bentonite, bone char, perlite, zeolite, hydrotalcite, silica gel, activated carbon.

In a preferred embodiment, the decoloring step is specifically that a decoloring agent is added into the clear liquid, the clear liquid is stirred uniformly and filtered, and the filtrate is collected; the color removing agent is an inorganic color removing agent and/or an organic color removing agent.

The second aspect of the invention provides application of a saponin composition with high stability, and the saponin composition is applied to the field of daily chemical products.

Has the advantages that:

the saponin composition obtained by the invention has the following advantages:

(1) the invention adopts the green and environment-friendly extraction method to efficiently extract the saponin composition from the plant raw materials, and the method has the advantages of low cost, simple and convenient process and strong feasibility, and is suitable for the field of natural surfactants;

(2) the method obviously improves the saponin purity of the soapberry peel extract by controlling a specific extraction process, further limits the selection of a flocculation adsorption material and a color removal agent in the extraction process, and improves the color stability of a saponin product; the transparent liquid is clear and transparent at the temperature of 25-60 ℃ and the pH value of 6-8, and can still keep stable color at the temperature of 25-50 ℃ after being placed for 7 days.

(3) The saponin composition prepared by the invention has excellent comprehensive performance, the stabilization time at 0 ℃ is more than 2 years, the stabilization time at room temperature is more than 1 year, and the stabilization time at 42 ℃ is more than 2 months; meanwhile, the paint has low irritation and high dirt-removing power, and the content of heavy metal meets the industrial specification.

Description of the drawings:

FIG. 1 is a schematic diagram of a process for preparing a saponin composition;

FIG. 2 is a schematic representation of a saponin composition obtained in example 1;

FIG. 3 is a schematic diagram of a saponin composition obtained in example 2.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

"Polymer" means a polymeric compound prepared by polymerizing monomers of the same or different types. The generic term "polymer" embraces the terms "homopolymer", "copolymer", "terpolymer" and "interpolymer". "interpolymer" means a polymer prepared by polymerizing at least two different monomers. The generic term "interpolymer" includes the term "copolymer" (which is generally used to refer to polymers prepared from two different monomers) and the term "terpolymer" (which is generally used to refer to polymers prepared from three different monomers). It also includes polymers made by polymerizing more monomers. "blend" means a polymer formed by two or more polymers being mixed together by physical or chemical means.

In order to solve the above problems, the present invention provides, in a first aspect, a saponin composition extracted from a natural plant; as shown in fig. 1, the specific extraction steps include:

s1, pretreating a natural plant;

s2, extracting the pretreated natural plant to obtain an extracting solution;

s3, clarifying the extracting solution to obtain a clarified solution;

s4, decolorizing the clarified liquid to obtain a decolorized liquid;

and S5, refining the decolorized solution to obtain a finished product.

In some preferred embodiments, the natural plant comprises at least one of soapberry, camellia japonica, honey locust, soapwort, quillaja saponaria, polygala tenuifolia, turmeric, ginseng, platycodon grandiflorum, bupleurum, anemarrhena asphodeloides bunge, and glycyrrhiza uralensis.

Further preferably, the natural plant includes at least one of soapberry, camellia japonica, gleditsia sinensis, soapwort and quillaja.

Still more preferably, the natural plant is soapberry peel.

In some preferred embodiments, the pretreatment step is to pulverize the natural plant to 3-100 mesh to obtain natural plant powder.

Further preferably, the natural plants are pretreated before being crushed; the pretreatment means is freeze hardening or microwave drying.

In some preferred embodiments, the extracting step is specifically that natural plant powder is dissolved in an extracting agent, stirred and filtered to obtain an extracting solution; the weight ratio of the natural plant powder to the extractant is 1: (1.5-4).

In some preferred embodiments, the extractant includes at least one of water, residue secondary filtrate, methanol, ethanol, acetone, n-butanol, and ethyl acetate.

In some preferred embodiments, the secondary filter solution of the filter residue is specifically prepared by dissolving natural plant powder in water, stirring at 45-65 ℃, performing solid-liquid separation, collecting the filter residue, re-dissolving in water, stirring at 45-65 ℃, performing solid-liquid separation again, and obtaining the liquid, namely the secondary filter solution of the filter residue.

Soapberry is a clean natural plant with high medicinal value and is used by people in daily life since ancient times. Modern analysis means shows that the soapberry peel contains abundant components such as saponin, vitamins and various organic acids, and the soapberry extract has the functions of environmental protection, cleaning and decontamination, antibiosis and skin care and the like, and becomes a popular product in daily chemical natural surfactants. At present, the extraction and purification method of the sapindus mukorossi pericarp is still in the initial stage in China, and the traditional extraction method comprises a solvent extraction method, an ultrasonic extraction method, a supercritical fluid extraction method, a microwave extraction method, an enzyme biological extraction method and the like, but the methods cannot meet the balance of the purity of the extract and the batch production capacity. According to the invention, a large number of experiments prove that the soapberry pericarp is extracted by a solvent extraction method, especially by secondary filtrate, so that the consumption of a large amount of organic solvent is avoided, the purity of the saponin compound in the soapberry pericarp can be improved, the cyclic utilization of all raw materials in the production process is realized, and the actual production efficiency of the saponin composition is improved. In the technical scheme of the invention, the secondary filtrate is a secondary steeping liquor of filter residue obtained after the soapberry pericarp is steeped by pure water, and compared with a pure water extraction mode and a small molecular organic reagent (such as methanol, ethanol, acetone and the like) extraction mode, the secondary steeping liquor has stronger extraction capacity of effective components of soapberry pericarp powder crushed after freezing crushing or microwave drying. According to the invention, the pretreatment of the soapberry pericarp is carried out, the process control at a lower temperature is adopted, the nutrient substances in the solid components are retained to the maximum extent, the secondary filter liquor of the filter residue in the extraction process permeates into the tissue cells of the soapberry pericarp powder, the soluble saponin composition is quickly dissolved and diffused into the secondary solvent, the secondary filter liquor of the filter residue and the target components in the soapberry pericarp powder in the process present strong similar intermiscibility characteristic, and the solid content and the saponin purity of the final product are both obviously improved. The scheme has important significance for actual production when the high-purity saponin composition is prepared, compared with the large waste of solid slag after traditional extraction, the method makes the best use of things, not only collects the extracting solution after each extraction, but also fully realizes the reutilization of the solid slag, realizes the circular operation of the preparation process of the saponin composition, and has higher practical application value.

In some preferred embodiments, the clarifying step is specifically to sequentially add a flocculating agent and a microporous material into the extracting solution, stir uniformly, and separate solid impurities to obtain a clarified solution; the weight ratio of the extracting solution, the flocculating agent and the microporous material is 1500-: 1-2: 40-230.

Further preferably, the weight ratio of the extracting solution, the flocculating agent and the microporous material is 1700-3900: 1-2: 50-200.

Still more preferably, the weight ratio of the extraction liquid, the flocculating agent and the microporous material is 1900: 1.5: 100.

in some preferred embodiments, the microporous material comprises at least one of diatomaceous earth, bentonite, bone char, perlite, zeolite, hydrotalcite, silica gel, activated carbon.

Further preferably, the microporous material is diatomite, bentonite and bone charcoal; the particle size of the microporous material is 50-800 meshes.

Still more preferably, the weight ratio of the diatomite, the bentonite and the bone charcoal is 5: (1-2): (0.5-2).

Although the solid content and the saponin purity of the product are improved by extracting the soapberry pericarp with the secondary filtrate, the impurity components such as alkaloid, glycosides, organic acids, protein, tannin and the like in the soapberry pericarp are leached out, and the color and the stability of the preparation are reduced. In the prior art, chitosan is usually used as a flocculating agent, and the cationic property of the chitosan is utilized to adsorb negative charge precipitates in a solution, so that the storage stability of a product is improved; however, chitosan has poor solubility and is limited by the pH environment of the medium, and thus, it is difficult to sufficiently exert the adsorption effect. According to the invention, polyquaternium, polyacrylamide and polyaluminium are used as flocculating agents, polymer molecular chains are topologically arranged in the extracting solution to form a cross-linked entanglement network with high charge density, and a specific capture effect is generated on impurity colloids and heavy metal ions in the extracting solution, so that the impurity colloids and heavy metal ions are separated from the solution system to form agglomerated flocs, the impurity content in the saponin composition after separation is obviously reduced, and the performance and color stability of the product are improved.

The invention further discovers that when the weight ratio of the extracting solution, the flocculating agent and the microporous material is 1500-: 1-2: 40-230, the purity and stability of the saponin composition can be further improved, probably because the flocculant and the microporous material can synergistically optimize the impurity removal effect under the proportion, and unstable impurity aggregates in the extracting solution are connected under the action of van der Waals force and chemical bonding force and are effectively stripped from the saponin composition system under the participation of an organic-inorganic bridging structure. Meanwhile, when the ionic degree of polyacrylamide is 50%, the surface tension of the soapberry aqueous extract is reduced to below 1%, the soapberry aqueous extract can be directionally arranged on the surface of the solution, the product has excellent cleaning effects on carbon black polluted cloth, protein polluted cloth and sebum polluted cloth, and the broad-spectrum cleaning effect of the saponin composition is improved.

In some preferred embodiments, the decolorizing step is specifically that a decolorizing agent is added into the clear liquid, the mixture is stirred uniformly and filtered, and the filtrate is collected; the color removing agent is an inorganic color removing agent and/or an organic color removing agent.

More preferably, the color remover is an inorganic color remover; the inorganic color removing agent is calcium hydroxide and sodium bisulfite.

In some preferred embodiments, the color remover is added and stirred and then the phosphoric acid is added for treatment.

More preferably, the weight ratio of the calcium hydroxide, the sodium bisulfite and the phosphoric acid is (20-40): 1: (3-10).

In some preferred embodiments, the refining step is specifically to purify the decolorized solution by electrodialysis or resin, and concentrate to obtain the finished saponin composition.

Based on the application scene of the surfactant, an excellent natural surface activity needs to have the capability of adapting to temperature change and medium environment change. The invention researches and discovers that after extraction and clarification, the temperature resistance and the pH tolerance of the surfactant can be obviously improved by selecting calcium hydroxide and sodium bisulfite as a decolorizer and cooperating with phosphoric acid; the reason may be that the color removing agent with specific components can reduce conjugated double bond groups such as-C ═ O-and the like in the clarified liquid to destroy chromophoric groups on the one hand, and on the other hand, metal ions in the color removing agent can form chelate or precipitate with impurities in the clarified liquid to further remove ineffective substances in the saponin composition, so that the saponin composition is refined to be a clear transparent liquid at the temperature of 25-60 ℃ and the pH value of 6-8, and can still keep stable color at the temperature of 25-50 ℃ after being placed for 7 days; the problems that insoluble substances are easy to precipitate and the transparency is reduced in the conventional preparation process of the saponin composition are solved.

In some preferred embodiments, the saponin composition comprises a triterpenoid saponin and a sesquiterpene glycoside.

The structural general formula of the triterpenoid saponin is as follows:

more preferably, the R1, R2, R3, R4, R5 and R6 may be the same or different.

Still more preferably, said R1, R2, R3, R4, R5, R6 may be selected from-H, -COC (CH)₃)＝CHCH₃，-OH，-CH₂OH，-CH₃，-OCOCH₂CH₂C₆H₅，-OCOC(CH₃)＝CHCH₃，-CHO，-COCH＝CHC₆H₅，-OCOCH₂(CH₃)CH₂CH₃One or more of beta-D-glucopyranosyl, beta-D-xylopyranosyl, alpha-L-rhamnopyranosyl and alpha-L-arabinopyranosyl.

In some preferred embodiments, the sesquiterpene glycoside has the general structural formula

Further preferably, R' can be selected from one or more of beta-D-glucopyranosyl, beta-D-xylopyranosyl, alpha-L-rhamnopyranosyl, alpha-L-arabinopyranosyl and hydrogen.

Further preferably, the saponin composition is applied to the field of green surfactants.

Examples

In order to better understand the above technical solutions, the following detailed descriptions will be provided with reference to specific embodiments. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. In addition, the raw materials are commercially available and the extraction methods of the extract are all conventional extraction methods, if not otherwise specified.

Example 1.

This example provides a saponin composition having high stability, which is extracted from the pericarp of soapberry; the specific extraction steps comprise:

s1, pretreatment: microwave drying the soapberry peel, taking out and crushing the soapberry peel into 50 meshes to obtain soapberry peel powder;

s2, extraction: putting 1000kg of soapberry peel powder into 2000kg of filter residue secondary filtrate, stirring for 2h at 60 ℃, performing plate-and-frame filter pressing, and collecting filtrate to obtain extract;

s3, clarification: adding 1.5kg of flocculant into 1900kg of extracting solution, and stirring for 2 hours at 50 ℃; then adding 100kg of microporous materials, stirring for 2 hours at 50 ℃, performing plate-and-frame filter pressing, and collecting filtrate I and filter residue I; adding 500kg of water into the first filter residue, stirring for 2 hours at 60 ℃, performing plate and frame filter pressing, and collecting a second filtrate; mixing the filtrate I and the filtrate II to obtain a clarified liquid;

s4, decoloring: adding 31kg of a decolorizing agent into 2300kg of the clarified liquid, stirring for 2h at 90 ℃, adding 5kg of phosphoric acid, stirring uniformly, filtering with 200-mesh filter cloth, collecting filtrate III, adding 1000kg of water into the filter residue III, stirring for 1h at 90 ℃, stirring uniformly, filtering with 200-mesh filter cloth again, collecting filtrate IV, combining the filtrate III and the filtrate IV, centrifuging the combined filtrate for 30min by using a tubular centrifuge, and collecting supernatant, namely decolorizing liquid;

s5, refining: removing impurities from the decolorized solution by using an electrodialysis device, and then concentrating the extracting solution by using a plate-type falling film evaporator.

The flocculating agent is polyquaternium, polyacrylamide and polyaluminium; the weight ratio of the polyquaternium, the anionic polyacrylamide and the polyaluminium is 1: 2: 2. the polyquaternium is purchased from boster chemical (shanghai) ltd under model No. PSC 60629; the ionic degree of the polyacrylamide is 50 percent, and the polyacrylamide is purchased from blue water purification materials, Inc. in Hiroshi city; polyaluminium was purchased from Shandong Xinhai purification technology, Inc. under the model number PAC 01.

The microporous material is diatomite, bentonite and bone charcoal; the weight ratio of the diatomite, the bentonite and the bone charcoal is 5: 1.5: 2. the diatomite is purchased from Henan' an vast water purification material Co., Ltd, and has the particle size of 325 meshes; the bentonite is purchased from Yiguo bentonite factory in Anji county, and the particle size is 200 meshes; the bone charcoal is purchased from Feilong bone charcoal Co., Ltd, Luo he city, and has a particle size of 400 meshes.

The color removing agent is calcium hydroxide and sodium bisulfite, and the weight ratio of the calcium hydroxide to the sodium bisulfite is 30: 1.

the preparation method of the filter residue secondary filtrate comprises the following steps: putting 1000kg of soapberry peel powder into 2000kg of distilled water, stirring for 2h at 60 ℃, and performing plate-and-frame filter pressing; adding 2000kg of solvent into the filter residue, stirring for 2h at 50 ℃, and performing plate-and-frame filter pressing again to obtain filtrate, namely secondary filter liquor of the filter residue.

The filter screen specification of plate frame filter pressing is 200 meshes.

The electrodialysis device is provided with 20 pairs of ion exchange membranes, the membrane area is 16cm multiplied by 18cm, and the total area is 0.612m²Voltage 50V; the evaporation capacity of the plate-type falling-film evaporator is 3000kg/h, and the evaporation area is 60m²。

Example 2.

s1, pretreatment: freezing the soapberry peel at-10 ℃ for 2h, taking out, and crushing the soapberry peel into 50 meshes to obtain soapberry peel powder;

s2, extraction: adding 1kg of soapberry peel powder into 2kg of distilled water, stirring for 2h at 50 ℃, centrifuging, adding 2L of distilled water at 50 ℃ into the solid intermediate product, keeping the temperature, stirring for 2h, centrifuging again, and combining the filtrates obtained by two times of centrifugation to obtain an extracting solution;

s3, clarification: adding 1.5g of flocculant into 3.7kg of extracting solution, and stirring for 2h at 50 ℃; then adding 50g of microporous material, stirring for 2h at 50 ℃, centrifuging, taking a solid intermediate product II, adding 1L of water, stirring for 2h at 60 ℃, centrifuging again, and combining filtrates obtained by two times of centrifugation to obtain a clarified liquid;

s4, decoloring: adding 31g of color removing agent into 4.5kg of clarified liquid, stirring for 2h at 90 ℃, adding 5g of phosphoric acid, uniformly stirring, filtering with 200-mesh filter cloth, adding 1L of water into filter residue, stirring for 1h at 90 ℃, uniformly stirring, filtering with 200-mesh filter cloth again, and combining the filtrates obtained by two times of filtration to obtain decolorized liquid;

s5, refining: adding 1kg of D101 macroporous adsorption resin into 4.5kg of decolorized solution, stirring for 2h at 40 ℃, performing suction filtration and collecting the resin, adding 4kg of ethanol aqueous solution with the volume fraction of 50% into the resin, stirring for 2h at 40 ℃, performing suction filtration again and collecting the resin, adding 3kg of ethanol aqueous solution with the volume ratio of 1: 1, eluting the mixture of ethanol and acetone, collecting eluent, and drying in vacuum to obtain the finished product.

example 3.

A saponin composition with high stability is provided, the specific implementation mode is the same as that of example 1; the difference is that the secondary filtrate of the filter residue is replaced by distilled water.

Example 4.

A saponin composition with high stability is provided, the specific implementation mode is the same as that of example 1; the difference is that the flocculating agent is aluminum sulfate.

Example 5.

A saponin composition with high stability is provided, the specific implementation mode is the same as that of example 1; the difference lies in that the weight ratio of the diatomite, the bentonite and the bone charcoal is 1: 1: 3.

example 6.

A saponin composition with high stability is provided, the specific implementation mode is the same as that of example 1; the difference is that the bone charcoal is replaced by zeolite, and the zeolite is purchased from Shijiazhuang Mazeo building materials Co., Ltd and has a particle size of 120 meshes.

Performance testing

1. Temperature and pH resistance test:

using the soapnut saponin obtained in example 1 as a test sample, adjusting pH to 6 +/-1.5 with hydrochloric acid or sodium hydroxide, and placing in a constant temperature box at 25 ℃, 40 ℃, 50 ℃ and 60 ℃ to test temperature resistance and pH tolerance of the test sample; the stronger the temperature and pH tolerance of the test sample, the higher the stability of the saponin composition is reflected. The results are as follows:

TABLE 1 temperature and pH tolerance results for example 1

2. Irritation:

the samples of examples 1 and 2 were tested for ocular irritancy using the RBC method (sheep red blood cell hemolysis test); specifically, the half hemolysis concentration HC50 and the hemoglobin denaturation index Di of the sheep red blood cells in vitro of the sample were measured, H/D was calculated as HC50/Di, and the ocular irritation of the sample was determined by the magnitude of the H/D value. Defining the relationship of H/D value to irritation as: H/D value > 100-no stimulation, H/D value > 10-micro stimulation, H/D value > 1-light stimulation, H/D value > 0.1-stimulation, H/D value < 0.1-very stimulation. The test results of example 1 were microstimulation, and the test results of example 2 were light stimulation.

TABLE 2 results of irritation test for examples 1-2

	HC50(mg/L)	Di	H/D value	Irritation property
					Example 1	400	25.7	15.6	Micro-stimulation
Example 2	60-80	21.2	2.8	Mild stimulation

3. Surface tension:

the equilibrium surface tension of the surfactant solution was measured by the platinum plate method. The method specifically comprises the following steps:

3.1 preparation of the samples

Preparing the water extract of the soapberry obtained in the example 1 (calculated by 100%) into an aqueous solution with the mass percentage of 0.1%, 0.5%, 1%, 2%, 4%, 5%, 8%, 10%, 15%, 20% and 25% by using deionized water as a solvent; the lyophilized powder of the sapindus mukorossi extract obtained in example 2 (calculated as 100%) was prepared into an aqueous solution of 0.05%, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 2%, 6%, 8%, 10%, 12% by mass. The mass of the extract and deionized water was weighed to an accuracy of 0.1 g.

3.2 calibrating surface tensiometer

The BYZ-1 surface tension meter power supply is turned on, and the calibration is carried out by using weights after the preheating is carried out for 30 minutes. The surface tension value of the deionized water is measured for 4 times, and the difference is not more than 2mN/m compared with the surface tension value of the pure water at the temperature in the appendix of an instrument manual.

3.3 measurement of surface tension of surfactant solutions

The measurements were repeated 2 times on the 3.1 prepared sample and readings were recorded with a difference of no more than 0.5 mN/m. The surfactant solutions of different concentrations were measured in order from low concentration to high concentration. Note that: after testing with a certain concentration of surfactant solution, the platinum plate must be thoroughly cleaned. The surface tension of the deionized water was then measured and compared to a measurement of 3.2 no more than 1 mN/m. Otherwise, the platinum plate is washed again until the requirement is met.

TABLE 3 surface tension test results for example 1 gradient samples

TABLE 4 surface tension test results for example 2 gradient samples

4. Decontamination capability:

the sample obtained in example 1 is prepared to be 0.2 wt% of test concentration (the solvent is water), the stain removal capability of the sample is tested by referring to QB/T1224-2012, and the result shows that the stain removal capability of the sample on carbon black stained cloth is better than that of alkyl benzene sulfonic acid; the detergency of the sample on the protein dirty cloth is equivalent to that of alkyl benzene sulfonic acid.

5. Solid content and purity:

the samples of examples 1-6 were tested for solids content using the baking method and the samples of examples 1-6 were tested for purity (g/g dry substance x 100%) using a uv spectrophotometer.

Taking the saponin compositions obtained in the embodiment 1 and the embodiments 3-6 as a sample to be tested, and sequentially standing at 5 ℃ for 3h, 25 ℃ for 3h and 50 ℃ for 3h, and circulating for 3 times; observing whether the tested sample has the phenomena of color change, layering and precipitation; each group of samples to be tested is divided into 10 parallel samples, and the number n of the parallel samples which have the phenomena of color change, delamination and sedimentation after the circulation is finished is recorded. When n is 0, the stability is good, n is more than 0 and less than or equal to 3, and n is more than 3, the stability is poor.

TABLE 5 test results for solids content, purity and stability of examples 1-6

	Solid content%	Purity%	Stability of
				Example 1	20	82	Superior food
Example 2	98	80	\
				Example 3	18	74	Superior food
Example 4	15	53	Difference (D)
				Example 5	16	62	Good wine
Example 6	14	57	Good wine

Finally, it is pointed out that the foregoing examples are illustrative only, serving to explain some of the characteristics of the process according to the invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims

1. A saponin composition with high stability is extracted from natural plants; the method is characterized by comprising the following specific extraction steps:

s1, pretreating the natural plants;

s2, extracting the natural plants after the pretreatment to obtain an extracting solution;

s3, clarifying the extracting solution to obtain a clarified solution;

s4, decoloring the clear liquid to obtain a decolored liquid;

s5, refining the decolored liquid to obtain a finished product;

the extraction step is specifically that natural plant powder is dissolved in an extracting agent, stirred and filtered to obtain an extracting solution; the weight ratio of the natural plant powder to the extractant is 1: (1.5-4);

the extracting agent comprises one of water and secondary filter liquid of filter residue;

dissolving natural plant powder in water, stirring at 45-65 ℃, carrying out solid-liquid separation, collecting filter residues, re-dissolving the filter residues in the water, stirring at 45-65 ℃, carrying out solid-liquid separation again, and obtaining a liquid, namely the filter residue secondary filtrate;

the clarification step is specifically that a flocculating agent and a microporous material are sequentially added into the extracting solution, the mixture is uniformly stirred, and solid impurities are separated to obtain a clarified solution; the weight ratio of the extracting solution, the flocculating agent and the microporous material is 1500-: 1-2: 40-230;

the flocculating agent is polyquaternium, polyacrylamide and polyaluminium; the weight ratio of the polyquaternium, the polyacrylamide and the polyaluminium is 1: 2: 2.

2. the saponin composition of claim 1, wherein the natural plant comprises at least one of soapberry, camellia, gleditsia sinensis, soapwort, quillaja, polygala tenuifolia, turmeric, ginseng, platycodon grandiflorum, bupleurum chinense, anemarrhena asphodeloides bunge, and glycyrrhiza uralensis.

3. A saponin composition with high stability according to claim 1 or 2, wherein the pre-treatment step is specifically to pulverize the natural plant to 3-100 mesh to obtain natural plant powder.

4. The saponin composition with high stability of claim 1, wherein the microporous material comprises at least one of diatomaceous earth, bentonite, bone charcoal, perlite, zeolite, hydrotalcite, silica gel, and activated carbon.

5. The saponin composition with high stability according to claim 1, wherein the decolorizing step comprises adding a decolorizing agent into the clarified solution, stirring, filtering, and collecting the filtrate; the color removing agent is an inorganic color removing agent and/or an organic color removing agent.

6. Use of a saponin composition with high stability according to any one of claims 1-5 in the field of daily chemicals.