WO2022268235A1 - 一种稳定性高的皂苷组合物及其应用 - Google Patents

一种稳定性高的皂苷组合物及其应用 Download PDF

Info

Publication number
WO2022268235A1
WO2022268235A1 PCT/CN2022/113842 CN2022113842W WO2022268235A1 WO 2022268235 A1 WO2022268235 A1 WO 2022268235A1 CN 2022113842 W CN2022113842 W CN 2022113842W WO 2022268235 A1 WO2022268235 A1 WO 2022268235A1
Authority
WO
WIPO (PCT)
Prior art keywords
saponin composition
extract
high stability
saponin
natural plant
Prior art date
Application number
PCT/CN2022/113842
Other languages
English (en)
French (fr)
Inventor
王孔江
辛亮
王颖
毛勇进
Original Assignee
广东菁萃生物科技有限公司
中国科学院生物物理研究所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 广东菁萃生物科技有限公司, 中国科学院生物物理研究所 filed Critical 广东菁萃生物科技有限公司
Publication of WO2022268235A1 publication Critical patent/WO2022268235A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • C07H1/06—Separation; Purification
    • C07H1/08—Separation; Purification from natural products
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/20—Carbocyclic rings
    • C07H15/203—Monocyclic carbocyclic rings other than cyclohexane rings; Bicyclic carbocyclic ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J63/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by expansion of only one ring by one or two atoms
    • C07J63/008—Expansion of ring D by one atom, e.g. D homo steroids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives

Definitions

  • the invention relates to the technical field of plant extraction, in particular to a saponin composition with high stability and application thereof.
  • Surfactant as an oil-water amphiphilic substance that can reduce the surface energy of reagents, is a major core raw material in the daily chemical industry. In 2015, the world's surfactant production was 21.2 million tons; it is estimated that by 2025, the output value of the world's surfactant market will reach 70 billion U.S. dollars, which has broad market development prospects.
  • Surfactants currently on the market can be divided into two categories: synthetic surfactants and green surfactants according to raw materials. The vast majority of synthetic surfactants come from petrochemicals, and the raw materials are organic reagents such as alkylbenzene and ethylene oxide.
  • Green surfactants are a type of surfactants produced by chemical synthesis of natural oils and plant-derived carbohydrates. Compared with synthetic surfactants, the advantages of this type of surfactants are low irritation and strong degradability , but there are still problems such as chemical residual risk and high cost.
  • saponin is one of them.
  • saponins have incomparable advantages over chemically synthesized surfactants: firstly, they have good biodegradability and can be rapidly degraded 100% in the natural environment; secondly, they are less irritating to human skin, mild in nature, and most The important thing is that the decontamination ability of saponins is better than that of sodium alkylbenzene sulfonate and other substances, and it has gradually replaced chemical synthetic surfactants.
  • Saponin is a kind of compound formed by the condensation of sugar and saponin.
  • saponins in plants such as pulp and acacia are very high, and the saponins in these plants are oleanane-type triterpene saponins; before the rise of the modern chemical industry, Sapindus fruit peel, tea meal, and acacia were used for daily washing for a long time .
  • sapindus fruit peel in Guangdong, Fujian, Hunan, Jiangxi, Guizhou and Sichuan in China exceeds 1 million mu.
  • the main purpose of sapindella fruit stone is oil extraction, and sapindora oil is used to prepare industrial diesel oil. Due to the long-term slump in international oil prices, the income of forest farmers who plant Sapindus fruit trees is quite limited. And 56% of the dry weight of Sapindus fruit is pericarp, and the saponin content of pericarp is about 30%.
  • there is still a lack of technology for industrialized extraction of sapindus saponin which is also a bottleneck restricting the development of sapindus saponin industry.
  • the defects in the prior art mainly contain the following points: 1. Dark color: the traditional Sapindus chinensis extraction method adds ethanol or n-butanol to extract after the raw material is pulverized, and the product obtained presents dark brown; Although it can prevent the color from getting darker, because the color of the Sapindus chinensis extract itself is dark reddish brown, the color of the final product is also reddish brown; 2.
  • the existing saponin extraction process often uses organic Solvent extraction of saponins, commonly used solvents include ethanol, methanol, n-butanol, etc.; after the first step of organic solvent extraction of saponins, the purity of saponins is higher than that of water, but the cost of solvents plus the price of raw materials causes saponin production The cost remains high, and it is difficult to put it into mass industrial production.
  • the present invention creatively provides a green and environment-friendly extraction process for extracting saponins from plant materials, which can solve all the above-mentioned problems.
  • the saponin composition provided by the invention has light color, high purity and strong stability, and can be widely used in daily chemical products.
  • the present invention solves the problem that the cost, purity and stability of existing natural surfactants are difficult to balance, and realizes a saponin composition with low cost, high efficiency and superior product performance .
  • the first aspect of the present invention provides a saponin composition, which is extracted from natural plants; the specific extraction steps include:
  • the natural plants include at least one of Sapindus chinensis, camellia, saponins, soapwort, soap tree, polygala, turmeric, ginseng, bellflower, bupleurum, anemarrhena, and licorice.
  • the pretreatment step specifically comprises: pulverizing the natural plant to 3-100 mesh to obtain natural plant powder.
  • the extraction step is specifically, dissolving the natural plant powder in the extractant, stirring and filtering to obtain the extract; the weight ratio of the natural plant powder to the extractant is 1:( 1.5-4).
  • the extractant includes at least one of water, secondary filtrate of filter residue, methanol, ethanol, acetone, n-butanol, and ethyl acetate.
  • the secondary filtrate of the filter residue is specifically, dissolving the natural plant powder in water, stirring at 45-65°C, separating the solid from the liquid, collecting the filter residue and redissolving it in water, and then Stir at 45-65°C, and then separate the solid and liquid again, and the obtained liquid is the secondary filtrate of the filter residue.
  • the clarification step specifically includes adding flocculant and microporous material to the extract in sequence, stirring evenly, separating solid impurities, and obtaining clarified liquid; extracting liquid, flocculant and microporous material
  • the weight ratio is 1500-4000:1-2:40-230.
  • the microporous material includes at least one of diatomite, bentonite, bone char, perlite, zeolite, hydrotalcite, silica gel, and activated carbon.
  • the decolorization step is specifically adding a decolorizing agent to the clear liquid, stirring evenly, filtering, and collecting the filtrate;
  • the decolorizing agent is an inorganic decolorizing agent and/or an organic decolorizing agent .
  • the second aspect of the present invention provides the application of a saponin composition with high stability, and the saponin composition is applied in the field of daily chemical products.
  • the present invention adopts a green and environment-friendly extraction method to efficiently extract the saponin composition from plant raw materials.
  • the method is low in cost, simple in process and strong in feasibility, and is suitable for the field of natural surfactants;
  • the present invention significantly improves the saponin purity of the Sapindus fruit peel extract through the control of a specific extraction process, further limits the selection of flocculation adsorption materials and color removers in the extraction process, and improves the color stability of the saponin product; It appears as a clear and transparent liquid in the range of 25-60°C and pH 6-8. After being placed for 7 days, it can still maintain a stable color at 25-50°C.
  • the saponin composition prepared by the present invention has excellent comprehensive properties, the stability time at 0°C exceeds 2 years, the stability time at room temperature exceeds 1 year, and the stability time at 42°C exceeds 2 months; at the same time, it exhibits low irritation and high detergency, And the heavy metal content is in line with industry norms.
  • Fig. 2. the physical figure of the saponin composition that embodiment 1 makes;
  • Fig. 3 the saponin composition material picture that embodiment 2 makes.
  • compositions, steps, method, article, or device comprising listed elements is not necessarily limited to those elements, but may include other elements not explicitly listed or inherent to such composition, step, method, article, or device. elements.
  • Polymer means a polymeric compound prepared by polymerizing monomers of the same or different type.
  • the generic term “polymer” encompasses the terms “homopolymer”, “copolymer”, “terpolymer” and “interpolymer”.
  • Interpolymer means a polymer prepared by polymerizing at least two different monomers.
  • the general term “interpolymer” includes the term “copolymer” (which is generally used to refer to a polymer prepared from two different monomers) and the term “terpolymer” (which is generally used to refer to a polymer prepared from three different monomers). of polymers). It also includes polymers made by polymerizing further monomers.
  • Blend means a polymer formed by mixing two or more polymers together by physical or chemical means.
  • the first aspect of the present invention provides a saponin composition, which is extracted from natural plants; as shown in Figure 1, the specific extraction steps include:
  • the natural plants include at least one of Sapindus chinensis, camellia, saponins, soapwort, soap tree, polygala, turmeric, ginseng, bellflower, bupleurum, anemarrhena, and licorice.
  • the natural plants include at least one of Sapindus chinensis, camellia, saponins, soapwort, and saponins.
  • the natural plant is Sapindus pericarp.
  • the pretreatment step specifically includes pulverizing the natural plants to 3-100 mesh to obtain natural plant powder.
  • the natural plants are pretreated before crushing; the pretreatment means are freeze hardening or microwave drying.
  • the extraction step is specifically, dissolving the natural plant powder in the extractant, stirring and filtering to obtain the extract; the weight ratio of the natural plant powder to the extractant is 1:(1.5 -4).
  • the extractant includes at least one of water, secondary filtrate of filter residue, methanol, ethanol, acetone, n-butanol, and ethyl acetate.
  • the secondary filtrate of the filter residue is specifically, dissolving the natural plant powder in water, stirring at 45-65°C, separating the solid from the liquid, collecting the filter residue and redissolving it in water at 45°C. Stir at -65°C, and separate the solid and liquid again, and the obtained liquid is the secondary filtrate of the filter residue.
  • Sapindus As a natural plant with high cleansing and medicinal value, Sapindus has been used daily by people since ancient times. Modern analysis methods show that the Sapindus fruit peel is rich in saponins, vitamins and various organic acids and other components. Popular products in . At present, the extraction and purification methods of Sapindus rind are still in their infancy in China. Traditional extraction methods include solvent extraction, ultrasonic extraction, supercritical fluid extraction, microwave extraction, and enzymatic biological extraction. The balance of extract purity and mass production capacity cannot be met.
  • the present invention finds that the solvent extraction method, especially the secondary filtrate, is used to extract Sapindus pericarp, which not only avoids the consumption of a large amount of organic solvents, but also can improve the purity of saponin compounds in Sapindus pericarp, and also The recycling of all raw materials in the production process is realized, and the actual production efficiency of the saponin composition is improved.
  • the secondary filtrate is the re-immersion liquid of the filter residue obtained after the Sapindus pericarp is immersed in pure water.
  • the present invention adopts a lower temperature process control when pre-treating the Sapindus pericarp, retains the nutrients in the solid components to the greatest extent, and the secondary filter liquid of the filter residue in the extraction process penetrates into the Sapindus pericarp powder tissue cells, The soluble saponin composition quickly dissolves and diffuses into the secondary solvent. During this process, the secondary filtrate of the filter residue and the target components in the Sapindus fruit peel powder show strong similar miscibility characteristics.
  • the clarification step is specifically, adding flocculant and microporous material to the extract in sequence, stirring evenly, separating solid impurities, and obtaining clarified liquid; the weight of extract, flocculant and microporous material The ratio is 1500-4000:1-2:40-230.
  • the weight ratio of the extract, flocculant and microporous material is 1700-3900:1-2:50-200.
  • the weight ratio of the extract, flocculant and microporous material is 1900:1.5:100.
  • the microporous material includes at least one of diatomite, bentonite, bone char, perlite, zeolite, hydrotalcite, silica gel, and activated carbon.
  • the microporous material is diatomite, bentonite and bone char; the particle size of the microporous material is 50-800 mesh.
  • the weight ratio of diatomite, bentonite and bone char is 5:(1-2):(0.5-2).
  • the use of the secondary filtrate to extract Sapindus pericarp improves the solid content and saponin purity of the product, it is accompanied by impurity components such as alkaloids, glycosides, organic acids, proteins, and tannins in Sapindus pericarp. Being leached, the color and stability of the preparation all decrease.
  • chitosan is often used as a flocculant, and the cationic properties of chitosan are used to absorb negatively charged precipitation in the solution to improve the storage stability of the product; however, the solubility of chitosan is very poor and is limited by the pH of the medium environment, the adsorption effect is difficult to fully exert.
  • the present invention uses polyquaternary ammonium salt, polyacrylamide and polyaluminum as flocculants, and the polymer molecular chains are topologically placed in the extract to form a cross-linked entanglement network with high charge density, which is specific for impurity colloids and heavy metal ions in the extract.
  • the property capture effect makes it separate from the solution system to form agglomerated flocs. After separation, the impurity content in the saponin composition is significantly reduced, and the performance and color stability of the product are improved.
  • the present invention further found that when the weight ratio of the extract, flocculant and microporous material is 1500-4000:1-2:40-230, the purity and stability of the saponin composition can be further improved, the reason may be that under this ratio
  • the flocculant and microporous material can synergistically optimize the impurity removal effect, and the unstable impurity aggregates in the extract are connected under the action of van der Waals force and chemical bonding force, and are effectively stripped off the saponin composition system with the participation of organic-inorganic bridging structure .
  • the decolorizing step specifically includes adding a decolorizing agent to the clear liquid, stirring evenly, filtering, and collecting the filtrate;
  • the decolorizing agent is an inorganic decolorizing agent and/or an organic decolorizing agent.
  • the color-removing agent is an inorganic color-removing agent; the inorganic color-removing agent is calcium hydroxide and sodium bisulfite.
  • phosphoric acid is added for treatment after adding the color removing agent and stirring.
  • the weight ratio of calcium hydroxide, sodium bisulfite, and phosphoric acid is (20-40):1:(3-10).
  • the refining step specifically includes using electrodialysis or resin to purify the decolorized solution, and concentrating to obtain a finished saponin composition.
  • an excellent natural surfactant needs to have the ability to adapt to changes in temperature and medium environment.
  • the stable color can still be maintained at 50°C; the problem that the conventionally prepared saponin composition is easy to precipitate insoluble substances and reduce the transparency during the standing process is improved.
  • the saponin composition includes triterpene saponins and sesquiterpene glycosides.
  • R1, R2, R3, R4, R5 and R6 may be the same or different.
  • the general structural formula of the sesquiterpene glycoside is
  • the R, R' can be selected from ⁇ -D-glucopyranosyl, ⁇ -D-xylopyranosyl, ⁇ -L-rhamnopyranosyl, ⁇ -L-arabinopyranosyl Glycosyl, one or more combinations of hydrogen.
  • the second aspect of the present invention provides the application of a saponin composition with high stability, and the saponin composition is applied in the field of daily chemical products.
  • the said saponin composition is applied in the field of green surfactants.
  • This embodiment provides a saponin composition with high stability, which is extracted from Sapindus sapindus pericarp; the specific extraction steps include:
  • the flocculant is polyquaternary ammonium salt, polyacrylamide and polyaluminum; the weight ratio of polyquaternium ammonium salt, anionic polyacrylamide and polyaluminum is 1:2:2.
  • the polyquaternium salt was purchased from Pushi Chemical (Shanghai) Co., Ltd., the model is PSC60629; the ionicity of polyacrylamide was 50%, purchased from Gongyi Lanyu Water Purification Material Co., Ltd.; polyaluminum was purchased from Shandong Xinhai Purification Technology Co., Ltd., model number PAC01.
  • the microporous material is diatomite, bentonite and bone char; the weight ratio of diatomite, bentonite and bone char is 5:1.5:2.
  • the diatomite was purchased from Henan Anmiao Water Purification Material Co., Ltd., with a particle size of 325 meshes; bentonite was purchased from Anji County Yiguo Bentonite Factory, with a particle size of 200 meshes; bone charcoal was purchased from Luohe Feilong Bone Carbon Co., Ltd. The particle size is 400 mesh.
  • the color removing agent is calcium hydroxide and sodium bisulfite, and the weight ratio of calcium hydroxide and sodium bisulfite is 30:1.
  • the preparation method of the secondary filtrate of the filter residue is as follows: put 1000 kg of sapindus fruit peel powder into 2000 kg of distilled water, stir at 60° C. for 2 hours, and press filter with plate and frame; add 2000 kg of solvent to the filter residue, stir at 50° C. for 2 hours, and plate and frame Pressure filtration, the resulting filtrate is the secondary filtrate of the filter residue.
  • the filter screen specification of the plate and frame filter press is 200 mesh.
  • the electrodialysis device is equipped with 20 pairs of ion exchange membranes, the membrane area is 16cm ⁇ 18cm, the total area is 0.612m 2 , and the voltage is 50V; the evaporation capacity of the plate falling film evaporator is 3000kg/h, and the evaporation area is 60m 2 .
  • This embodiment provides a saponin composition with high stability, which is extracted from Sapindus sapindus pericarp; the specific extraction steps include:
  • Pre-treatment freeze the sapindilla fruit peel at -10°C for 2 hours, take it out and crush the sapindella fruit peel into 50 meshes to obtain the sapindella fruit peel powder;
  • Clarification add 1.5g flocculant to 3.7kg extract, stir at 50°C for 2h; then add 50g of microporous material, stir at 50°C for 2h, centrifuge, take the solid intermediate product 2, add 1L water, stir at 60°C for 2h, again Centrifuge, and combine the filtrate of two centrifuges, which is the clarified liquid;
  • the flocculant is polyquaternary ammonium salt, polyacrylamide and polyaluminum; the weight ratio of polyquaternium ammonium salt, anionic polyacrylamide and polyaluminum is 1:2:2.
  • the polyquaternium salt was purchased from Pushi Chemical (Shanghai) Co., Ltd., the model is PSC60629; the ionicity of polyacrylamide was 50%, purchased from Gongyi Lanyu Water Purification Material Co., Ltd.; polyaluminum was purchased from Shandong Xinhai Purification Technology Co., Ltd., model number PAC01.
  • the microporous material is diatomite, bentonite and bone char; the weight ratio of diatomite, bentonite and bone char is 5:1.5:2.
  • the diatomite was purchased from Henan Anmiao Water Purification Material Co., Ltd., with a particle size of 325 meshes; bentonite was purchased from Anji County Yiguo Bentonite Factory, with a particle size of 200 meshes; bone charcoal was purchased from Luohe Feilong Bone Carbon Co., Ltd. The particle size is 400 mesh.
  • the color removing agent is calcium hydroxide and sodium bisulfite, and the weight ratio of calcium hydroxide and sodium bisulfite is 30:1.
  • a saponin composition with high stability the specific implementation method is the same as that of Example 1; the difference is that the secondary filtrate of the filter residue is replaced by distilled water.
  • a saponin composition with high stability the specific implementation method is the same as in Example 1; the difference is that the flocculant is aluminum sulfate.
  • a saponin composition with high stability the specific implementation method is the same as in Example 1; the difference is that the weight ratio of diatomite, bentonite and bone char is 1:1:3.
  • a saponin composition with high stability 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 Mayue Building Materials Co., Ltd., with a particle size of 120 mesh.
  • Example 1 Take the Sapindus saponin obtained in Example 1 as the test sample, adjust the pH to 6 ⁇ 1.5 with hydrochloric acid or sodium hydroxide, and place it in a thermostat at 25°C, 40°C, 50°C, and 60°C to determine the tested sample.
  • the temperature resistance and pH tolerance test of the sample the stronger the temperature resistance and pH tolerance of the tested sample, the higher the stability of the saponin composition is reflected. The result is as follows:
  • H/D value and irritation as follows: H/D value>100-no stimulation, H/D value>10-slight stimulation, H/D value>1-light stimulation, H/D value>0.1-stimulation , H/D value ⁇ 0.1 - very irritating.
  • the test result of embodiment 1 is slight stimulation, and the test result of embodiment 2 is light stimulation.
  • the equilibrium surface tension of the surfactant solution was measured by the platinum plate method. Specifically:
  • Use deionized water as solvent to be made into mass percent by embodiment 1 gained Sapindus chinensis aqueous extract (in 100%) and be 0.1%, 0.5%, 1%, 2%, 4%, 5%, 8%, 10% %, 15%, 20%, 25% aqueous solution; it is 0.05%, 0.1%, 0.2%, 0.5%, 0.8% by mass percentage to be made into the lyophilized powder of Sapindus chinensis extract obtained in Example 2 (calculated as 100%) %, 1%, 1.2%, 1.5%, 2%, 6%, 8%, 10%, 12% aqueous solution. Accurate to 0.1g when weighing the extract and deionized water.
  • the solid content of the samples of Examples 1-6 was tested by a drying method, and the purity of the samples of Examples 1-6 was tested by an ultraviolet spectrophotometer (g/g dry matter ⁇ 100%).
  • Example 1 and Examples 3-6 Using the saponin composition obtained in Example 1 and Examples 3-6 as the test sample, place it at 5°C for 3h, at 25°C for 3h, and at 50°C for 3h, and cycle 3 times; observe whether the test sample has discoloration, Delamination and precipitation phenomenon; each group of tested samples is divided into 10 parallel samples, and the number n of parallel samples with discoloration, delamination and precipitation phenomena after the cycle is recorded.
  • n 0 as excellent stability, 0 ⁇ n ⁇ 3 as good stability, and n>3 as poor stability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Biotechnology (AREA)
  • Genetics & Genomics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Cosmetics (AREA)

Abstract

本发明涉及植物提取技术领域，尤其涉及一种稳定性高的皂苷组合物及其制备方法。所述皂苷组合物提取自天然植物；具体提取步骤包括：S1.对天然植物进行前处理；S2.对前处理后的天然植物进行提取，得到提取液；S3.对提取液进行澄清，得到澄清液；S4.对澄清液进行脱色，得到脱色液；S5.对脱色液进行精制，得到成品。本发明得到的皂苷组合物具有以下优点：(1)本发明采用绿色环保的提取方法，从植物原料中高效提取皂苷组合物，该方法成本低，工艺简便，可行性强，适合在天然表面活性剂领域；(2)本发明制得的皂苷组合物纯度高，颜色稳定性强；(3)本发明制得的皂苷组合物综合性能优异，具有低刺激性、高去污能力，且重金属含量符合行业规范。

Description

一种稳定性高的皂苷组合物及其应用 技术领域
本发明涉及植物提取技术领域，尤其涉及一种稳定性高的皂苷组合物及其应用。
背景技术
表面活性剂作为一种具有降低试剂表面能作用的油水两亲性物质，是日化产业的大宗核心原料。2015年全世界表面活性剂产量为2120万吨；预计2025，世界表面活性剂市场的产值可高达七百亿美元，具有广阔的市场发展前景。目前市场上的表面活性剂按照原料可以划分为合成表面活性剂和绿色表面活性剂两大类，合成表面活性剂绝大多数来源于石油化工，原料为烷基苯、环氧乙烷等有机试剂，容易造成水体、土壤污染，并且这类表面活性剂对皮肤的刺激性强，对环境和人体有潜在的健康危害。绿色表面活性剂是由天然油脂、植物来源的碳水化合物，经过化工合成生产的一类表面活性剂，与合成表面活性剂相比，这类表面活性剂的优势是刺激性低，可降解性强，但是仍然存在着化学残留风险和成本高昂弊端等问题。
纯天然非合成的表面活性剂生产技术尚未成熟，天然存在的表面活性剂中，能够用于日化产品的选择寥寥无几，皂苷正是其中之一。作为天然表面活性剂的代表，皂苷具有化工合成的表面活性剂不可比拟的优势：首先生物降解性好，在自然环境中可迅速100％降解，其次对人体皮肤的刺激性低，性质温和，最重要的是皂苷的去污能力优于烷基苯磺酸钠等物质，已有逐渐替代化工合成表面活性剂之势。皂苷是一类由糖和皂苷元缩合而成的化合物，在天然植物中以混合物的形式存在，作为山茶属、无患子属和皂荚属植物的主要次级代谢产物，无患子果皮、茶粕、皂荚等植物中的皂苷含量非常高，这些植物中的皂苷为齐墩果烷型三萜皂苷；在近代化学工业兴起以前，无患子果皮、茶粕、皂荚长期被用于日用洗涤。
目前无患子果皮在中国广东、福建、湖南、江西、贵州及四川等地的种植规模超过100万亩。无患子果核的主要用途是榨油，无患子油用于制备工业柴油。由于国际油价长期低迷，种植无患子果树的林农的收益相当有限。而无患子果实 干重的56％是果皮，果皮的皂苷含量约为30％。但是目前还缺乏工业化提取无患子皂苷的技术，这也是制约无患子产业发展的瓶颈。现有的皂苷提取技术存在很多缺陷，既不能工业化大规模生产，也无法大量应用于日化产品。现有技术中的缺陷主要有以下几点：1.颜色深：传统无患子提取方法将原料粉碎后加入乙醇或正丁醇提取，得到的产物呈现深棕色；而在提取过程中加入抗氧化剂虽然可以防止颜色变深，但由于无患子提取液本身颜色是深红棕色，所以最终产品的颜色也是红棕色；2.稳定性差：现有皂苷提取液的纯度较低，提取液中含有蛋白质、多酚和果胶等成分，这些成分会互相作用，存放时间不长就会产生沉淀，或是不可逆的颜色变深，难以长期储存；3.成本高：现有的皂苷提取工艺往往使用有机溶剂提取皂苷，常用溶剂有乙醇、甲醇、正丁醇等；有机溶剂提取皂苷的第一步提取以后，皂苷的纯度相比水提更高，但溶剂的成本再加上原料的价格造成皂苷生产成本居高不下，难以投入批量化工业生产。
技术问题
现有技术中还未出现能够同时解决颜色、纯度、成本等问题的技术方案，所以现在市场上日化产品中的纯天然植物表面活性剂产品，或颜色呈深棕色，稳定性差；或只添加少量无患子或茶枯提取物，主要表面活性剂还是化工合成表面活性剂。在这样的背景下，本发明创造性地提供一种绿色环保的提取工艺，从植物原料中提取皂苷，能解决上述所有问题。本发明提供的皂苷组合物颜色浅、纯度高、稳定性强，可以广泛应用于日化产品中。
技术解决方案
本发明通过提供一种稳定性高的皂苷组合物，解决了现有天然表面活性剂成本、纯度、稳定性难以兼顾的问题，实现了一种成本低，效率高，产品性能优越的皂苷组合物。
本发明第一方面提供了一种皂苷组合物，所述皂苷组合物提取自天然植物；具体提取步骤包括：
S1.对天然植物进行前处理；
S2.对前处理后的天然植物进行提取，得到提取液；
S3.对提取液进行澄清，得到澄清液；
S4.对澄清液进行脱色，得到脱色液；
S5.对脱色液进行精制，得到成品。
在一种优选的实施方式中，所述天然植物包括无患子，山茶，皂荚，肥皂草，皂树，远志，黄姜，人参，桔梗，柴胡，知母，甘草中的至少一种。
在一种优选的实施方式中，所述前处理步骤具体为，将天然植物粉碎至3-100目，得到天然植物粉体。
在一种优选的实施方式中，所述提取步骤具体为，将天然植物粉体溶解于提取剂中，搅拌过滤，得到提取液；所述天然植物粉体和提取剂的重量比为1：(1.5-4)。
在一种优选的实施方式中，所述提取剂包括水，滤渣二次过滤液，甲醇，乙醇，丙酮，正丁醇，乙酸乙酯中的至少一种。
在一种优选的实施方式中，所述滤渣二次过滤液具体为，将天然植物粉体溶解于水中，在45-65℃条件下搅拌，固液分离，收集滤渣并重新溶解于水中，在45-65℃条件下搅拌，再次固液分离，所得的液体即为滤渣二次过滤液。
在一种优选的实施方式中，所述澄清步骤具体为，向提取液中依次加入絮凝剂和微孔材料，搅拌均匀，分离固体杂质，得到澄清液；提取液，絮凝剂和微孔材料的重量比为1500-4000：1-2：40-230。
在一种优选的实施方式中，所述微孔材料包括硅藻土，膨润土，骨炭，珍珠岩，沸石，水滑石，硅胶，活性炭中的至少一种。
在一种优选的实施方式中，所述脱色步骤具体为，向澄清液中加入除色剂，搅拌均匀，过滤，收集滤液；所述除色剂为无机除色剂和/或有机除色剂。
本发明第二方面提供了一种稳定性高的皂苷组合物的应用，所述皂苷组合物应用于日化用品领域。
有益效果
本发明得到的皂苷组合物具有以下优点：
(1)本发明采用绿色环保的提取方法，从植物原料中高效提取皂苷组合物，该方法成本低，工艺简便，可行性强，适合在天然表面活性剂领域；
(2)本发明通过特定提取工艺的控制，显著提升了无患子果皮提取物的皂苷纯度，进一步限定提取过程中絮凝吸附材料以及除色剂的选择，提高了皂苷产物的色泽稳定性；在25～60℃、pH为6～8范围内呈现为澄清透明液体，在放置7天后，在25～50℃下仍能保持稳定色泽。
(3)本发明制得的皂苷组合物综合性能优异，0℃稳定时间超过2年，室温 稳定时间超过1年，42℃稳定时间超过2个月；同时呈现低刺激性、高去污能力，且重金属含量符合行业规范。
附图说明
图1.皂苷组合物的制备工艺示意图；
图2.实施例1制得的皂苷组合物实物图；
图3.实施例2制得的皂苷组合物实物图。
本发明的实施方式
参选以下本发明的优选实施方法的详述以及包括的实施例可更容易地理解本发明的内容。除非另有限定，本文使用的所有技术以及科学术语具有与本发明所属领域普通技术人员通常理解的相同的含义。当存在矛盾时，以本说明书中的定义为准。
如本文所用术语“由…制备”与“包含”同义。本文中所用的术语“包含”、“包括”、“具有”、“含有”或其任何其它变形，意在覆盖非排它性的包括。例如，包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素，而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。
连接词“由…组成”排除任何未指出的要素、步骤或组分。如果用于权利要求中，此短语将使权利要求为封闭式，使其不包含除那些描述的材料以外的材料，但与其相关的常规杂质除外。当短语“由…组成”出现在权利要求主体的子句中而不是紧接在主题之后时，其仅限定在该子句中描述的要素；其它要素并不被排除在作为整体的所述权利要求之外。
当量、浓度、或者其它值或参数以范围、优选范围、或一系列上限优选值和下限优选值限定的范围表示时，这应当被理解为具体公开了由任何范围上限或优选值与任何范围下限或优选值的任一配对所形成的所有范围，而不论该范围是否单独公开了。例如，当公开了范围“1至5”时，所描述的范围应被解释为包括范围“1至4”、“1至3”、“1至2”、“1至2和4至5”、“1至3和5”等。当数值范围在本文中被描述时，除非另外说明，否则该范围意图包括其端值和在该范围内的所有整数和分数。
单数形式包括复数讨论对象，除非上下文中另外清楚地指明。“任选的”或者“任意一种”是指其后描述的事项或事件可以发生或不发生，而且该描述包括 事件发生的情形和事件不发生的情形。
说明书和权利要求书中的近似用语用来修饰数量，表示本发明并不限定于该具体数量，还包括与该数量接近的可接受的而不会导致相关基本功能的改变的修正的部分。相应的，用“大约”、“约”等修饰一个数值，意为本发明不限于该精确数值。在某些例子中，近似用语可能对应于测量数值的仪器的精度。在本申请说明书和权利要求书中，范围限定可以组合和/或互换，如果没有另外说明这些范围包括其间所含有的所有子范围。
此外，本发明要素或组分前的不定冠词“一种”和“一个”对要素或组分的数量要求(即出现次数)无限制性。因此“一个”或“一种”应被解读为包括一个或至少一个，并且单数形式的要素或组分也包括复数形式，除非所述数量明显旨指单数形式。
“聚合物”意指通过聚合相同或不同类型的单体所制备的聚合化合物。通用术语“聚合物”包含术语“均聚物”、“共聚物”、“三元共聚物”与“共聚体”。“共聚体”意指通过聚合至少两种不同单体制备的聚合物。通用术语“共聚体”包括术语“共聚物”(其一般用以指由两种不同单体制备的聚合物)与术语“三元共聚物”(其一般用以指由三种不同单体制备的聚合物)。其亦包含通过聚合更多种单体而制造的聚合物。“共混物”意指两种或两种以上聚合物通过物理的或化学的方法共同混合而形成的聚合物。
为了解决上述问题，本发明第一方面提供了一种皂苷组合物，所述皂苷组合物提取自天然植物；如图1所示，具体提取步骤包括：
S1.对天然植物进行前处理；
S2.对前处理后的天然植物进行提取，得到提取液；
S3.对提取液进行澄清，得到澄清液；
S4.对澄清液进行脱色，得到脱色液；
S5.对脱色液进行精制，得到成品。
在一些优选的实施方式中，所述天然植物包括无患子，山茶，皂荚，肥皂草，皂树，远志，黄姜，人参，桔梗，柴胡，知母，甘草中的至少一种。
进一步优选，所述天然植物包括无患子，山茶，皂荚，肥皂草，皂树中的至少一种。
更进一步优选，所述天然植物为无患子果皮。
在一些优选的实施方式中，所述前处理步骤具体为，将天然植物粉碎至3-100目，得到天然植物粉体。
进一步优选，粉碎前对天然植物进行预处理；预处理手段为冷冻硬化或微波干燥。
在一些优选的实施方式中，所述提取步骤具体为，将天然植物粉体溶解于提取剂中，搅拌过滤，得到提取液；所述天然植物粉体和提取剂的重量比为1：(1.5-4)。
在一些优选的实施方式中，所述提取剂包括水，滤渣二次过滤液，甲醇，乙醇，丙酮，正丁醇，乙酸乙酯中的至少一种。
在一些优选的实施方式中，所述滤渣二次过滤液具体为，将天然植物粉体溶解于水中，在45-65℃条件下搅拌，固液分离，收集滤渣并重新溶解于水中，在45-65℃条件下搅拌，再次固液分离，所得的液体即为滤渣二次过滤液。
无患子作为一种清洁、药用价值极高的天然植物，自古以来为人们日常所用。现代分析手段显示，无患子果皮中含有丰富的皂苷、维生素以及多种有机酸等成分，无患子提取物具有绿色环保、清洁去污、抗菌护肤等功能，已成为日化天然表面活性剂中的热门产品。目前国内对于无患子果皮的提取和提纯方法仍处于起步阶段，传统的提取方法包括溶剂提取法、超声波提取法、超临界流体提取法、微波提取法、酶生物提取法等，但这些方法均无法满足提取物纯度和批量生产能力的平衡。本发明通过大量实验探究发现，采用溶剂提取法，尤其是采用二次滤液对无患子果皮进行提取，既避免了大量有机溶剂的消耗，同时能够提高无患子果皮中皂苷化合物的纯度，还实现了生产工艺过程中所有原料的循环利用，提高了皂苷组合物的实际生产效率。在本发明技术方案中，所述二次滤液为无患子果皮经过纯水浸渍后所得滤渣的再次浸渍液，相比于纯水提取和小分子有机试剂(如甲醇，乙醇，丙酮等)提取方式，其对于冷冻粉碎或微波干燥后粉碎的无患子果皮粉体具有更强的有效成分提取能力。本发明在对无患子果皮进行前处理时采取较低温度的工艺控制，最大程度保留固体成分中的营养物质，提取过程中滤渣二次过滤液渗透进入无患子果皮粉体组织细胞中，可溶性皂苷组合物迅速溶解扩散至二次溶剂中，这一过程中滤渣二次过滤液与无患子果皮粉体中目标成分呈现出较强的相似相溶特性，终产物的固含量及皂苷纯度均明显提升。在制得高纯度皂苷组合物的同时，该方案对于实际生产也有着重要意义，相比于传统提取 后固体渣料的大量浪费，本发明物尽其用，每一次提取后不仅收集提取液，还充分实现固体渣料的再次利用，实现皂苷组合物制备工艺的循环运行，实际应用价值较高。
在一些优选的实施方式中，所述澄清步骤具体为，向提取液中依次加入絮凝剂和微孔材料，搅拌均匀，分离固体杂质，得到澄清液；提取液，絮凝剂和微孔材料的重量比为1500-4000：1-2：40-230。
进一步优选，所述提取液，絮凝剂和微孔材料的重量比为1700-3900：1-2：50-200。
更进一步优选，所述提取液，絮凝剂和微孔材料的重量比为1900：1.5：100。
在一些优选的实施方式中，所述微孔材料包括硅藻土，膨润土，骨炭，珍珠岩，沸石，水滑石，硅胶，活性炭中的至少一种。
进一步优选，所述微孔材料为硅藻土，膨润土和骨炭；微孔材料的粒径为50-800目。
更进一步优选，所述硅藻土，膨润土和骨炭的重量比为5：(1-2)：(0.5-2)。
采用二次滤液提取无患子果皮虽然提升了产物的固含量和皂苷纯度，但是伴随而来的是无患子果皮中的生物碱、苷类、有机酸类、蛋白质、鞣质等杂质成分同样被浸出，制剂的色泽和稳定性均出现下降。现有技术常使用壳聚糖作为絮凝剂，利用壳聚糖的阳离子特性吸附溶液中的负电荷沉淀，提高产物的储存稳定性；但是壳聚糖的溶解性很差，受限于介质的pH环境，吸附作用难以充分发挥。本发明采用聚季铵盐，聚丙烯酰胺和聚铝作为絮凝剂，聚合物分子链拓扑于提取液中，形成电荷密度高的交联缠结网络，对提取液中杂质胶体和重金属离子产生特异性捕捉作用，使得其脱离溶液体系形成团聚态絮凝物，分离之后皂苷组合物中杂质含量显著降低，产物的性能、色泽稳定性提升。
本发明进一步发现，当提取液，絮凝剂和微孔材料的重量比为1500-4000：1-2：40-230时，能够进一步提高皂苷组合物的纯度和稳定性，原因可能是该比例下絮凝剂和微孔材料能够协同优化除杂效果，提取液中的不稳定杂质凝聚体在范德华力和化学键合力的作用下连接，在有机-无机架桥结构的参与下被有效剥离皂苷组合物体系。同时发现，当聚丙烯酰胺的离子度为50％时，无患子水提物的表面张力降低至1％以下，能够在溶液表面定向排列，产物对碳黑污布、蛋白污布、皮脂污布均有优异清洁效果，皂苷组合物的广谱清洁效果提升。
在一些优选的实施方式中，所述脱色步骤具体为，向澄清液中加入除色剂，搅拌均匀，过滤，收集滤液；所述除色剂为无机除色剂和/或有机除色剂。
进一步优选，所述除色剂为无机除色剂；所述无机除色剂为氢氧化钙和亚硫酸氢钠。
在一些优选的实施方式中，加入除色剂搅拌后加入磷酸进行处理。
进一步优选，所述氢氧化钙，亚硫酸氢钠，磷酸的重量比为(20-40)：1：(3-10)。
在一些优选的实施方式中，所述精制步骤具体为，采用电渗析或树脂纯化脱色液，浓缩，得到皂苷组合物成品。
基于表面活性剂的应用场景，一款优异的天然表活需具备适应温度变化和介质环境变化的能力。本发明探究发现，在经过提取、澄清之后，选择氢氧化钙和亚硫酸氢钠作为除色剂，配合磷酸共同作用，能够显著提高表面活性剂的耐温性和pH耐受性；原因可能是特定成分除色剂一方面能够还原澄清液中的-C＝O-等双键共轭基团，破坏发色基团，另一方面除色剂中金属离子能与澄清液中的杂质形成螯合物或沉淀，进一步去除皂苷组合物中的无效物质，使得皂苷组合物经过精制之后，在25～60℃、pH为6～8范围内呈现为澄清透明液体，在放置7天后，在25～50℃下仍能保持稳定色泽；改善了常规制备的皂苷组合物在放置过程中容易析出不溶物质、透明度降低的问题。
在一些优选的实施方式中，所述皂苷组合物包括三萜皂苷和倍半萜糖苷。
所述三萜皂苷的结构通式为：
Figure PCTCN2022113842-appb-000001
进一步优选，所述R1，R2，R3，R4，R5，R6可以相同，也可以不同。
更进一步优选，所述R1，R2，R3，R4，R5，R6可以选自-H，-COC(CH 3)＝CHCH 3，-OH，-CH 2OH，-CH 3，-OCOCH 2CH 2C 6H 5，-OCOC(CH 3)＝CHCH 3，-CHO，-COCH＝CHC 6H 5，-OCOCH 2(CH 3)CH 2CH 3，β-D-吡喃葡萄搪基，β-D-吡喃木糖基，α-L-吡喃鼠李糖基，α-L-吡喃阿拉伯糖基中的一种或多种的组合。
在一些优选的实施方式中，所述倍半萜糖苷的结构通式为
Figure PCTCN2022113842-appb-000002
进一步优选，所述R，R’可以选自β-D-吡喃葡萄搪基，β-D-吡喃木糖基，α-L-吡喃鼠李糖基，α-L-吡喃阿拉伯糖基，氢中的一种或多种的组合。
本发明第二方面提供了一种稳定性高的皂苷组合物的应用，所述皂苷组合物应用于日化用品领域。
进一步优选，所述所述皂苷组合物应用于绿色表面活性剂领域。
实施例
为了更好的理解上述技术方案，下面将结合具体的实施方式对上述技术方案进行详细的说明。有必要在此指出的是，以下实施例只用于对本发明作进一步说明，不能理解为对本发明保护范围的限制，该领域的专业技术人员根据上述本发明的内容做出的一些非本质的改进和调整，仍属于本发明的保护范围。另外，如果没有其它说明，所用原料都是市售的，所述提取物的提取方法均为常规的提取方法。
实施例1.
本实施例提供了一种稳定性高的皂苷组合物，所述皂苷组合物提取自无患子果皮；具体提取步骤包括：
S1.前处理：将无患子果皮微波干燥，取出后将无患子果皮粉碎为50目，得到无患子果皮粉体；
S2.提取：将1000kg无患子果皮粉体投入2000kg滤渣二次过滤液中，在60℃条件下搅拌2h，板框压滤，收集滤液，即为提取液；
S3.澄清：向1900kg提取液中加入1.5kg絮凝剂，50℃搅拌2h；然后加入100kg微孔材料，50℃搅拌2h，板框压滤，收集滤液一和滤渣一；向滤渣一中加入500kg水，60℃搅拌2h，板框压滤，收集滤液二；合并滤液一和滤液二，得到澄清液；
S4.脱色：向2300kg澄清液中加入31kg除色剂，在90℃条件下搅拌2h，再加入5kg磷酸，搅拌均匀，200目滤布过滤，收集滤液三，取滤渣三加入1000kg水，在90℃条件下搅拌1h，搅拌均匀，再次进行200目滤布过滤，收集滤液四，并将滤液三和滤液四合并，采用管式离心机将合并后滤液离心30min，收集上清液，即为脱色液；
S5.精制：采用电渗析装置对脱色液进行除杂，然后用板式降膜蒸发器浓缩 提取液。
所述絮凝剂为聚季铵盐，聚丙烯酰胺和聚铝；聚季铵盐，阴离子聚丙烯酰胺和聚铝的重量比为1：2：2。所述聚季铵盐购买自浦仕化学(上海)有限公司，型号为PSC60629；聚丙烯酰胺的离子度为50％，购买自巩义市蓝宇净水材料有限公司；聚铝购买自山东信海净化科技有限公司，型号为PAC01。
所述微孔材料为硅藻土，膨润土和骨炭；硅藻土，膨润土和骨炭的重量比为5：1.5：2。所述硅藻土购买自河南安淼净水材料有限公司，粒径为325目；膨润土购买自安吉县益国膨润土厂，粒径为200目；骨炭购买自漯河市飞隆骨碳有限公司，粒径为400目。
所述除色剂为氢氧化钙和亚硫酸氢钠，氢氧化钙和亚硫酸氢钠的重量比为30：1。
所述滤渣二次过滤液的制备方法为：将1000kg无患子果皮粉体投入2000kg蒸馏水中，60℃搅拌2h，板框压滤；在滤渣中加入2000kg溶剂，50℃搅拌2h，再次板框压滤，所得滤液即为滤渣二次过滤液。
所述板框压滤的滤网规格为200目。
所述电渗析装置设置有20对离子交换膜，膜面积为16cm×18cm，总面积0.612m 2，电压50V；所述板式降膜蒸发器的蒸发量3000kg/h，蒸发面积60m 2。
实施例2.
本实施例提供了一种稳定性高的皂苷组合物，所述皂苷组合物提取自无患子果皮；具体提取步骤包括：
S1.前处理：将无患子果皮置于-10℃冷冻2h，取出后将无患子果皮粉碎为50目，得到无患子果皮粉体；
S2.提取：将1kg无患子果皮粉体投入2kg蒸馏水中，在50℃条件下搅拌2h，离心，取固体中间产物加入2L 50℃蒸馏水，保温搅拌2h，再次离心，合并两次离心的滤液，即为提取液；
S3.澄清：向3.7kg提取液中加入1.5g絮凝剂，50℃搅拌2h；然后加入50g微孔材料，50℃搅拌2h，离心，取固体中间产物二加入1L水，60℃搅拌2h，再次离心，合并两次离心的滤液，即为澄清液；
S4.脱色：向4.5kg澄清液中加入31g除色剂，在90℃条件下搅拌2h，再加入5g磷酸，搅拌均匀，200目滤布过滤，取滤渣加入1L水，在90℃条件下搅 拌1h，搅拌均匀，再次进行200目滤布过滤，合并两次过滤的滤液，即为脱色液；
S5.精制：向4.5kg脱色液中加入1kg D101大孔吸附树脂，40℃搅拌2h，抽滤并收集树脂，向树脂中加入4kg体积分数为50％的乙醇水溶液，40℃搅拌2h，再次抽滤并收集树脂，向树脂中加入3kg体积比为1：1的乙醇和丙酮混合物进行洗脱，收集洗脱液真空干燥，即为成品。
所述絮凝剂为聚季铵盐，聚丙烯酰胺和聚铝；聚季铵盐，阴离子聚丙烯酰胺和聚铝的重量比为1：2：2。所述聚季铵盐购买自浦仕化学(上海)有限公司，型号为PSC60629；聚丙烯酰胺的离子度为50％，购买自巩义市蓝宇净水材料有限公司；聚铝购买自山东信海净化科技有限公司，型号为PAC01。
所述微孔材料为硅藻土，膨润土和骨炭；硅藻土，膨润土和骨炭的重量比为5：1.5：2。所述硅藻土购买自河南安淼净水材料有限公司，粒径为325目；膨润土购买自安吉县益国膨润土厂，粒径为200目；骨炭购买自漯河市飞隆骨碳有限公司，粒径为400目。
所述除色剂为氢氧化钙和亚硫酸氢钠，氢氧化钙和亚硫酸氢钠的重量比为30：1。
实施例3.
一种稳定性高的皂苷组合物，具体实施方式同实施例1；不同点在于，将滤渣二次过滤液替换为蒸馏水。
实施例4.
一种稳定性高的皂苷组合物，具体实施方式同实施例1；不同点在于，所述絮凝剂为硫酸铝。
实施例5.
一种稳定性高的皂苷组合物，具体实施方式同实施例1；不同点在于，所述硅藻土，膨润土和骨炭的重量比为1：1：3。
实施例6.
一种稳定性高的皂苷组合物，具体实施方式同实施例1；不同点在于，将骨炭替换为沸石，沸石购买自石家庄马跃建材有限公司，粒径为120目。
性能测试
1.耐温性和pH耐受性测试：
以实施例1所得的无患子皂苷为被试样品，用盐酸或氢氧化钠调节pH为6±1.5，并放置在25℃、40℃、50℃、60℃的恒温箱内测定被试样品的耐温性和pH耐受性测试；被试样品的耐温性和pH耐受性越强，反应了皂苷组合物的稳定性越高。结果如下：
表1.实施例1的耐温性和pH耐受性结果
Figure PCTCN2022113842-appb-000003
Figure PCTCN2022113842-appb-000004
Figure PCTCN2022113842-appb-000005
2.刺激性：
采用RBC法(绵羊红细胞溶血试验)检测实施例1和实施例2试样的眼刺激性；具体为测定试样的体外绵羊红细胞的半数溶血浓度HC50以及血红蛋白变性指数Di值，计算H/D＝HC50/Di，通过H/D值的大小对样品的眼刺激性进行判定。定义H/D值与刺激性的关系为：H/D值＞100-无刺激，H/D值＞10-微刺激，H/D值＞1-轻刺激，H/D值＞0.1-刺激，H/D值＜0.1-非常刺激。实施例1的测试结果为微刺激，实施例2的测试结果为轻刺激。
表2.实施例1-2的刺激性测试结果
  HC50(mg/L) Di H/D值 刺激性
实施例1 400 25.7 15.6 微刺激
实施例2 60-80 21.2 2.8 轻刺激
3.表面张力：
采用白金板法测量表面活性剂溶液的平衡态表面张力。具体为：
3.1试样配制
用去离子水作为溶剂将实施例1所得无患子水提物(以100％计)配成质量百分比为0.1％、0.5％、1％、2％、4％、5％、8％、10％、15％、20％、25％的水溶液；将实施例2所得无患子提取物冻干粉(以100％计)配成质量百分比为0.05％、0.1％、0.2％、0.5％、0.8％、1％、1.2％、1.5％、2％、6％、8％、10％、12％的水溶液。称量提取物和去离子水质量时准确到0.1g。
3.2校准表面张力仪
打开BYZ-1表面张力仪电源，预热30分钟后用砝码校准。测量去离子水的表面张力值，测量4次，并对照仪器手册附录该温度下纯水的表面张力值，相差不应超过2mN/m。
3.3测量表面活性剂溶液的表面张力
对3.1制得的试样重复测量2次，记录读数，读数之差不大于0.5mN/m。不同浓度的表面活性剂溶液按从低浓度到高浓度的顺序进行测量。注意：在一定浓度的表面活性剂溶液测试完后，必须充分清洗白金板。然后测量去离子水的表面张力值，测量值和3.2的测量值相比不超过1mN/m。否则要重新冲洗白金板直到符合要求。
表3.实施例1梯度试样的表面张力测试结果
Figure PCTCN2022113842-appb-000006
Figure PCTCN2022113842-appb-000007
表4.实施例2梯度试样的表面张力测试结果
Figure PCTCN2022113842-appb-000008
4.去污能力：
取实施例1所得试样配制为0.2wt％试验浓度(溶剂为水)，参考QB/T1224-2012测试试样的去污能力，结果显示试样对炭黑污布的去污力优于烷基苯磺酸的去污力；试样对蛋白污布的去污力与烷基苯磺酸的去污力相当。
5.固含量和纯度：
采用烘干法测试实施例1-6试样的固含量，采用紫外分光光度计测试实施例1-6试样的纯度(g/g干物质×100％)。
以实施例1和实施例3-6所得的皂苷组合物为被试样品，依次于5℃放置3h，25℃放置3h、50℃放置3h，循环3次；观察被测试样是否出现变色、分层、沉淀现象；每组被测试样分为10个平行样品，记录循环结束后出现变色、分层、沉淀现象的平行样品个数n。定义n＝0为稳定性优，0＜n≤3为稳定性良，n＞3 为稳定性差。
表5.实施例1-6的固含量、纯度和稳定性测试结果
  固含量％ 纯度％ 稳定性
实施例1 20 82 优
实施例2 98 80 \
实施例3 18 74 优
实施例4 15 53 差
实施例5 16 62 良
实施例6 14 57 良
最后指出，前述的实例仅是说明性的，用于解释本发明所述方法的一些特征。所附的权利要求旨在要求可以设想的尽可能广的范围，且本文所呈现的实施例仅是根据所有可能的实施例的组合的选择的实施方式的说明。因此，申请人的用意是所附的权利要求不被说明本发明的特征的示例的选择限制。在权利要求中所用的一些数值范围也包括了在其之内的子范围，这些范围中的变化也应在可能的情况下解释为被所附的权利要求覆盖。

Claims (10)

  1. 一种稳定性高的皂苷组合物，所述皂苷组合物提取自天然植物；其特征在于，具体提取步骤包括：
    S1.对天然植物进行前处理；
    S2.对前处理后的天然植物进行提取，得到提取液；
    S3.对提取液进行澄清，得到澄清液；
    S4.对澄清液进行脱色，得到脱色液；
    S5.对脱色液进行精制，得到成品。
  2. 根据权利要求1所述的一种稳定性高的皂苷组合物，其特征在于，所述天然植物包括无患子，山茶，皂荚，肥皂草，皂树，远志，黄姜，人参，桔梗，柴胡，知母，甘草中的至少一种。
  3. 根据权利要求1或2所述的一种稳定性高的皂苷组合物，其特征在于，所述前处理步骤具体为，将天然植物粉碎至3-100目，得到天然植物粉体。
  4. 根据权利要求1所述的一种稳定性高的皂苷组合物，其特征在于，所述提取步骤具体为，将天然植物粉体溶解于提取剂中，搅拌过滤，得到提取液；所述天然植物粉体和提取剂的重量比为1：(1.5-4)。
  5. 根据权利要求4所述的一种稳定性高的皂苷组合物，其特征在于，所述提取剂包括水，滤渣二次过滤液，甲醇，乙醇，丙酮，正丁醇，乙酸乙酯中的至少一种。
  6. 根据权利要求5所述的一种稳定性高的皂苷组合物，其特征在于，所述滤渣二次过滤液具体为，将天然植物粉体溶解于水中，在45-65℃条件下搅拌，固液分离，收集滤渣并重新溶解于水中，在45-65℃条件下搅拌，再次固液分离，所得的液体即为滤渣二次过滤液。
  7. 根据权利要求1-3任一项所述的一种稳定性高的皂苷组合物，其特征在于，所述澄清步骤具体为，向提取液中依次加入絮凝剂和微孔材料，搅拌均匀，分离固体杂质，得到澄清液；提取液，絮凝剂和微孔材料的重量比为1500-4000：1-2：40-230。
  8. 根据权利要求8所述的一种稳定性高的皂苷组合物，其特征在于，所述微孔材料包括硅藻土，膨润土，骨炭，珍珠岩，沸石，水滑石，硅胶，活性炭中的至少一种。
  9. 根据权利要求1所述的一种稳定性高的皂苷组合物，其特征在于，所述脱色步骤具体为，向澄清液中加入除色剂，搅拌均匀，过滤，收集滤液；所述除色剂为无机除色剂和/或有机除色剂。
  10. 一种根据权利要求1-9任一项所述的稳定性高的皂苷组合物的应用，其特征在于，所述皂苷组合物应用于日化用品领域。
PCT/CN2022/113842 2021-06-23 2022-08-22 一种稳定性高的皂苷组合物及其应用 WO2022268235A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110698266.8A CN113546574B (zh) 2021-06-23 2021-06-23 一种稳定性高的皂苷组合物及其应用
CN202110698266.8 2021-06-23

Publications (1)

Publication Number Publication Date
WO2022268235A1 true WO2022268235A1 (zh) 2022-12-29

Family

ID=78130809

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/113842 WO2022268235A1 (zh) 2021-06-23 2022-08-22 一种稳定性高的皂苷组合物及其应用

Country Status (2)

Country Link
CN (1) CN113546574B (zh)
WO (1) WO2022268235A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113546574B (zh) * 2021-06-23 2022-04-12 广东菁萃生物科技有限公司 一种稳定性高的皂苷组合物及其应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102180935A (zh) * 2011-03-15 2011-09-14 湖南汉清生物技术有限公司 一种制备高纯度油茶皂甙的方法
CN102241725A (zh) * 2010-05-13 2011-11-16 福建源华林业生物科技有限公司 日化用无患子皂苷的水提制备方法
CN102617695A (zh) * 2012-03-08 2012-08-01 华南理工大学 一种脱糖脱色无患子皂苷及其制备方法
CN104211749A (zh) * 2014-08-15 2014-12-17 中山大学 一种无患子皂苷的生产工艺
CN104788526A (zh) * 2015-03-23 2015-07-22 福建省轻工业研究所 一种含澄清稳定复配物的无患子皂苷液及其制备方法
CN110407890A (zh) * 2019-07-18 2019-11-05 佛山市欧若拉生物科技有限公司 无患子皂苷的制备方法
CN113546574A (zh) * 2021-06-23 2021-10-26 广东菁萃生物科技有限公司 一种稳定性高的皂苷组合物及其应用

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0181226B1 (en) * 1984-11-08 1990-01-17 Canon Kabushiki Kaisha Method for purification of dyes
US5627273A (en) * 1995-01-31 1997-05-06 National Starch And Chemical Investment Holding Corporation Method for preparing hydrophobically-terminated polysaccharide polymers and detergent compositions comprising the polysaccharide polymers
EP1690834A3 (de) * 2005-02-14 2015-05-13 Sachtleben Chemie GmbH Polyaluminiumchloridlösung
CN101054221A (zh) * 2006-04-13 2007-10-17 萨克特本化学有限责任公司 聚合氯化铝溶液
LT2689774T (lt) * 2011-03-21 2019-03-25 Broda Technologies Co., Ltd Atvirkščiai termiškai grįžtama hidrogelio kompozicija
CN102260316A (zh) * 2011-05-23 2011-11-30 井冈山茶油有限公司 一种油茶籽饼粕中提纯茶皂素的方法
CN102250681B (zh) * 2011-06-20 2012-10-31 江南大学 一种从油茶籽中提取油茶籽油和茶皂素的方法
EP2873701A4 (en) * 2012-07-10 2016-01-06 Nippon Soda Co ORGANIC-INORGANIC COMPLEX, AND COMPOSITION FOR THE FORMATION OF SAID COMPLEX
CN103304621A (zh) * 2013-06-06 2013-09-18 湖南新泰裕农业科技投资有限公司 一种从油茶籽饼粕中提取高纯茶皂素的工艺
CN107072237B (zh) * 2014-09-02 2021-12-14 谱赛科有限责任公司 甜菊提取物
CN104744532A (zh) * 2015-04-03 2015-07-01 泉州市奈斯材料科技有限公司 一种无患子皂苷的提取精制的方法
CN106309540A (zh) * 2015-07-01 2017-01-11 四川小叶本草生物科技有限公司 一种滇皂荚总皂苷提取纯化的方法
CN105461778A (zh) * 2015-10-29 2016-04-06 广东星汇生物科技有限公司 一种从油茶枯中提取茶皂素的方法
EP3661998B1 (en) * 2017-07-31 2024-06-05 Ecolab USA Inc. Process for fast dissolution of powder comprising low molecular weight acrylamide-based polymer
CN109234037A (zh) * 2018-10-23 2019-01-18 广东举林农业科技股份有限公司 一种茶枯粉及其制备工艺

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102241725A (zh) * 2010-05-13 2011-11-16 福建源华林业生物科技有限公司 日化用无患子皂苷的水提制备方法
CN102180935A (zh) * 2011-03-15 2011-09-14 湖南汉清生物技术有限公司 一种制备高纯度油茶皂甙的方法
CN102617695A (zh) * 2012-03-08 2012-08-01 华南理工大学 一种脱糖脱色无患子皂苷及其制备方法
CN104211749A (zh) * 2014-08-15 2014-12-17 中山大学 一种无患子皂苷的生产工艺
CN104788526A (zh) * 2015-03-23 2015-07-22 福建省轻工业研究所 一种含澄清稳定复配物的无患子皂苷液及其制备方法
CN110407890A (zh) * 2019-07-18 2019-11-05 佛山市欧若拉生物科技有限公司 无患子皂苷的制备方法
CN113546574A (zh) * 2021-06-23 2021-10-26 广东菁萃生物科技有限公司 一种稳定性高的皂苷组合物及其应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YU LING: "Study on the New Technology of Water Extraction of Sapindus Sapindoside", THE LIGHT & TEXTILE INDUSTRIES OF FUJIAN, no. 5, 25 May 2013 (2013-05-25), pages 27 - 30, XP093016592, ISSN: 1007-550X *
ZHANG, CUI ET AL.: "Purification of sapindus-saponin by Aspergillus oryzae fermentation", GONGYE WEISHENGWU = INDUSTRIAL MICROBIOLOGY, SHANGHAI GONGYE WEISHENGWU YANJIUSUO, CN, vol. 42, no. 05, 22 October 2012 (2012-10-22), CN , pages 40 - 45, XP009542020, ISSN: 1001-6678 *

Also Published As

Publication number Publication date
CN113546574B (zh) 2022-04-12
CN113546574A (zh) 2021-10-26

Similar Documents

Publication Publication Date Title
CN101519458B (zh) 一种从粗老绿茶中提取茶多糖和茶多酚的方法
CN100491404C (zh) 芦荟多糖分级提取方法
WO2022268235A1 (zh) 一种稳定性高的皂苷组合物及其应用
Hu et al. Polysaccharides from pineapple pomace: new insight into ultrasonic-cellulase synergistic extraction and hypoglycemic activities
CN101580555A (zh) 一种不同分子量范围的岩藻多糖的制备方法
CN112569155B (zh) 一种欧蓍草提取物的提取方法及应用
CN101564650B (zh) 陶瓷膜清洗剂及其制备方法和应用
CN101906169B (zh) 一种白芨多糖制备的工艺组合
CN113698506A (zh) 一种温度响应型低共熔溶剂及提取枸杞多糖的方法
CN112220726A (zh) 一种释放远红外兼保湿沐浴露及其制备方法
CN108273291A (zh) 1+1澄清方法
CN107722083A (zh) 一种甜菊糖的高效生产工艺
CN106632725B (zh) 一种从果胶原料漂洗液中分离水溶性果胶的方法
CN104771713B (zh) 一种桑姜浸膏及其制备工艺和应用
CN104672350A (zh) 一种用于半纤维素生产的秸秆预处理方法
CN108066228B (zh) 一种保湿抗菌沐浴露及其制备方法
WO2023082422A1 (zh) 一种含左旋龙脑的复方冷制皂及其制备方法
CN111592578B (zh) 山茶粕中的茶皂素提取工艺及其在氨基酸洁面皂中的应用
CN115569158A (zh) 一种利用超声波辅助低共熔溶剂提取技术从番石榴叶中提取总黄酮的提取方法
CN107698693B (zh) 一种水果多糖脱色方法
CN102229755A (zh) 一种紫甘薯红色素的生产方法
CN117126225B (zh) 一种化学絮凝-超临界二氧化碳技术联用浸提高活性茶皂素的方法
CN112028962A (zh) 一种积雪草总苷的提取工艺
CN104592317A (zh) 一种雪莲果低聚果糖及其制备方法
CN116076641A (zh) 一种酸浆闪释粉及其制备方法和应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22827727

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22827727

Country of ref document: EP

Kind code of ref document: A1