CN113956322A - Method for removing harmful substances in momordica grosvenori extract - Google Patents

Abstract

The invention provides a method for removing harmful substances in a grosvenor momordica extract, which comprises the following steps of A) dissolving the grosvenor momordica extract, and carrying out enzymolysis to obtain an enzymolysis solution; B) adding alkali into the solution after enzymolysis to adjust the pH value, adding a chelating agent for reaction, and concentrating and drying after reaction to obtain a dry product; C) eluting the dried product by using alkaline alcohol, and collecting the eluent; D) evaporating and concentrating the eluent, loading onto macroporous adsorbent resin column, eluting, desorbing, collecting desorption solution, concentrating, and drying. Through the process, the pesticide residue, heavy metal, organic solvent and plasticization can be simultaneously removed, and the process is simple and has strong industrialization capability.

Description

Method for removing harmful substances in momordica grosvenori extract

Technical Field

The invention relates to the technical field of harmful substance removal, in particular to a method for removing harmful substances in a momordica grosvenori extract.

Background

Momordica grosvenori begins to be loaded into Chinese pharmacopoeia in 1977, and belongs to medicinal and edible traditional Chinese medicinal materials. The traditional Chinese medicine considers that the momordica grosvenori is sweet and sour in taste, cool in nature, and capable of entering lung and large intestine channels, and has the effects of clearing heat, moistening lung, moistening throat, relieving cough, moistening intestines, relaxing bowels and the like. It is used for treating lung heat dry cough, pharyngalgia aphonia, intestinal dryness constipation, etc. The momordica grosvenori has good health-care efficacy, and can clear heat, cool blood, promote the production of body fluid, relieve cough, smooth intestines, expel toxin, tender skin, benefit face, moisten lung, reduce phlegm, prolong life, preserve youthful looks and beautify.

The extract of momordica grosvenori (the main component of momordica grosvenori glycoside) is widely noticed and used in the fields of food, health care products, medicines and the like as a new generation of natural sweetener. At present, the variety of health-care food taking the momordica grosvenori extract as the sugar substitute is less, and the main products are momordica grosvenori juice, momordica grosvenori cake, herbal tea, yoghourt, beverage, dairy products, chocolate, ice cream, moon cake and the like. The momordica grosvenori extract is used as a sugar substitute, and is used for developing momordica grosvenori light drinks, cakes, milk tea, chocolate, soft sweets, beverages and other foods, so that the momordica grosvenori light drink has a very wide market prospect and profound and remote significance. The fructus momordicae extract is suitable for high-end people who pay attention to health and pay attention to life quality, and people who have or worry about hyperglycemia, obesity and decayed teeth.

The momordica grosvenori extract is used as a plant extract, the main raw material is from momordica grosvenori, and pesticides can be sprayed to prevent insects and diseases during planting, so that the pesticide residue problem of a final product can be directly caused; meanwhile, due to soil acidification caused by excessive use of chemistry, the activity of ionic heavy metal is enhanced, so that heavy metal enrichment effect is generated by plants, and finally the heavy metal of the product can exceed the standard; meanwhile, the product is accompanied with the problem of plasticizer and organic solvent residue in the extraction and separation process. These harmful substances, if not further removed, can eventually enter the food, thereby posing a safety risk to the food.

Taking the limit standards of pesticide residues of traditional Chinese medicinal materials as examples, 70 maximum residual quantities of 105 pesticides related to organic chlorine, organic phosphorus, pyrethroids and the like are formulated in European pharmacopoeia (EP8.0, United states Pharmacopeia (USP38) and British pharmacopoeia (BP 2015)), the limit standards and detection methods of heavy metals and pesticide residues in traditional Chinese medicinal materials are published in 2007 by the Korean food and medicine Security agency, 42 maximum residual limit standards related to 48 pesticides are formulated in total, furthermore, a positive list system of residual pesticides in food is implemented in 2006, which is called as a positive list system for short, wherein related agricultural chemicals mainly comprise pesticides, and 734 pesticides specified by only the temporary limit standard relate to 50000 residues.

The European pharmacopoeia and the United states pharmacopoeia are the most limited indexes of pesticide residue in traditional Chinese medicinal materials at present, and the limited indexes of pesticide residue in European Union botanical drugs are relatively perfect. The limited standards of pesticide residue in korea and japan are relatively low in the european union and the united states. The establishment of the limit standard of pesticide residues of Chinese medicinal materials is late, the covered medicinal material varieties are relatively few, and the related pesticide varieties are limited. The maximum residue limit of 22 organochlorine pesticides is specified in the Chinese pharmacopoeia of 2015 edition, while the related pesticide residue limit is specified only under the terms of ginseng, American ginseng, liquorice, astragalus root, ginseng stem leaf total saponin and ginseng total saponin in the standard body. In addition to the Chinese pharmacopoeia, the other Chinese related plant pesticide residue limit standard is WM/T2-2004 the Green industry Standard of Chinese medicinal plant and preparation foreign trade, which stipulates that the total content of hexachloro-cyclohexane is less than or equal to 0.1mg/kg, the content of dichlorodiphenyl is less than or equal to 0.1mg/kg, and the content of aldrin is less than or equal to 0.02 mg/kg. Therefore, compared with the pesticide residue limit of the traditional Chinese medicinal materials in foreign countries, the relevant standards and regulations in China still have much work to be perfected.

Mogroside, also known as Lo Han Guo extract, is sold primarily in the United states, Canada of North America; british, france, germany, switzerland, italy in europe, etc.; japan, korea, indonesia of asia; developed countries such as Australia and New Zealand in the oceans. People eat food as day and eat food as first. Therefore, how to remove harmful substances in the momordica grosvenori extract more effectively and improve the international trade export of the momordica grosvenori extract is very important.

There are some disclosures in the prior art relating to the removal of harmful substances: CN106306991 discloses a method for simultaneously removing pesticide residues and a plasticizer from a fructus momordicae extract, which is obtained by carbon dioxide supercritical extraction, water dissolution, nanofiltration and spray drying. The process needs supercritical equipment, has high industrialization difficulty, and can not effectively remove organic solvents and heavy metals. CN112694947 discloses a method for removing phthalate plasticizers from edible oil, which is to add additives to edible oil to extract plasticizers, and this method may cause secondary pollution of additives. In the method, pesticide residues, heavy metals, organic solvents and plasticizers cannot be removed simultaneously at one time, and some processes have extremely high requirements on equipment and operation and have great industrialization difficulty; some processes remove certain harmful substances and reflect other harmful substances to cause secondary pollution.

Therefore, the method for removing the harmful substances in the momordica grosvenori extract is developed, can simultaneously remove pesticide residues, heavy metals, organic solvents and plasticization, has simple process and strong industrialization capability, and has very important significance for improving the product quality, ensuring the food safety and expanding the international export trade market.

Disclosure of Invention

In view of the above, the technical problem to be solved by the present invention is to provide a method for removing harmful substances from a luo han guo extract, which can simultaneously remove pesticide residues, heavy metals, organic solvents and plasticization, and has a simple method and a good effect.

The invention provides a method for removing harmful substances in a momordica grosvenori extract, which comprises the following steps:

A) dissolving fructus Siraitiae Grosvenorii extract, and performing enzymolysis to obtain solution after enzymolysis;

B) adding alkali into the solution after enzymolysis to adjust the pH value, adding a chelating agent for reaction, and concentrating and drying after reaction to obtain a dry product;

C) eluting the dried product by using alkaline alcohol, and collecting the eluent;

D) evaporating and concentrating the eluent, loading onto macroporous adsorbent resin column, eluting, desorbing, collecting desorption solution, concentrating, and drying.

Preferably, the mogroside V content in the momordica grosvenori extract in the step A) is 3.5-90%.

Preferably, the enzyme of step a) is an organophosphorus degrading enzyme; the unit of enzyme activity is 1-20 ten thousand U/g; the fructus momordicae extract: enzyme: the mass ratio of water is 1: 0.01-0.08: 25-40;

the dissolving is carried out by adding water, and the dissolving temperature is 30-60 ℃.

Preferably, the chelating agent in the step B) is any one of EDTA or EDTA disodium; the added mass of the chelating agent is 0.5-1% of that of the grosvenor momordica extract.

Preferably, the alkali in the step B) is any one of sodium hydroxide or potassium hydroxide; the pH value is 8-10;

the concentration is carried out until the solid content is 15 to 30 percent.

Preferably, the basic alcohol in step C) is sodium ethoxide, potassium ethoxide, sodium methoxide or potassium methoxide; the mass ratio of the alkaline alcohol to the fructus momordicae extract is (6-10): 1; (ii) a The volume fraction of the basic alcohol is more than 95%.

Preferably, the step C) is specifically: placing the dried product in a chromatographic column, eluting by using alkaline alcohol, and collecting eluent; the height ratio of the chromatographic column diameter is 1: 5-10; the flow rate of the column washing is 0.5-1 bv/h;

preferably, the macroporous adsorption resin column in the step D) is any one of D101, AB-8, X-5, DM130, D101C, LX-100B, LX-T28 and LX-T81;

the height ratio of the diameter of the macroporous adsorption resin column is 1: 3-7; the flow rate of the macroporous absorption resin column is 0.5 bv/h.

Preferably, the column washing step D) is specifically: sequentially using an alkaline solvent, an acidic solvent and subcritical water to wash the column; the volumes of the alkaline solvent, the acidic solvent and the subcritical water washing column are independently selected from 3-6 bv; the flow rate of the column washing is 1-2 bv/h.

Preferably, the alkaline solvent is an alkaline aqueous solution containing a surfactant; the alkaline aqueous solution is a sodium hydroxide aqueous solution with the mass fraction of 0.3-1%;

the acid solvent is an acid aqueous solution containing a surfactant; the acidic aqueous solution is 0.3-1% of hydrochloric acid aqueous solution by mass;

the surfactant is ammonium phosphatide, propylene glycol fatty acid ester, propylene glycol alginate, succinic acid monoglyceride, polyglycerol ricinoleate, polyglycerol fatty acid ester, polyoxyethylene xylitol anhydride monostearate, polyoxyethylene sorbitan monolaurate, xylitol anhydride monostearate, citric acid fatty glyceride, hydrogenated rosin glyceride, lactic acid fatty glyceride, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sucrose fatty acid ester, modified soybean phosphatide, enzymolysis soybean phosphatide, acetylation monoglyceride fatty acid ester, acetylation diglycerol fatty acid ester; preferably diacetyl tartaric acid ester of mono-di-glycerides and/or acetylated mono-glycerides fatty acids;

the addition amount of the surfactant is 0.01-0.1 wt%;

the subcritical water is pure water with the temperature of 130-200 ℃ and the pressure of 15-20 MPa;

preferably, the desorbed solvent in step D) is an alcohol; the alcohol is ethanol or methanol; the volume fraction of the alcohols is 65-80%; the desorption flow rate is 0.5-1.5 bv/h; the using amount of the alcohols is 3-4 bv;

the drying is specifically that after the negative pressure drying is carried out to constant weight, the drying is carried out to constant weight under normal pressure, and the steps are alternated for 2-3 times;

the negative pressure drying is vacuum microwave drying or vacuum drying; the drying temperature is 140-160 ℃, and the vacuum degree is-0.07 to-0.1 MPa; the drying time is 1-2 h, and the drying time under normal pressure is 1-2 h.

Compared with the prior art, the invention provides a method for removing harmful substances in a grosvenor momordica extract, which comprises the following steps of A) dissolving the grosvenor momordica extract, and carrying out enzymolysis to obtain an enzymolysis solution; B) adding alkali into the solution after enzymolysis to adjust the pH value, adding a chelating agent for reaction, and concentrating and drying after reaction to obtain a dry product; C) eluting the dried product by using alkaline alcohol, and collecting the eluent; D) evaporating and concentrating the eluent, loading onto macroporous adsorbent resin column, eluting, desorbing, collecting desorption solution, concentrating, and drying. Through the process, the pesticide residue, heavy metal, organic solvent and plasticization can be simultaneously removed, and the process is simple and has strong industrialization capability.

Detailed Description

The invention provides a method for removing harmful substances in a fructus momordicae extract, and a person skilled in the art can appropriately improve process parameters by referring to the content. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.

The invention provides a method for removing harmful substances in a momordica grosvenori extract, which comprises the following steps:

A) dissolving fructus Siraitiae Grosvenorii extract, and performing enzymolysis to obtain solution after enzymolysis;

B) adding alkali into the solution after enzymolysis to adjust the pH value, adding a chelating agent for reaction, and concentrating and drying after reaction to obtain a dry product;

C) eluting the dried product by using alkaline alcohol, and collecting the eluent;

D) evaporating and concentrating the eluent, loading onto macroporous adsorbent resin column, eluting, desorbing, collecting desorption solution, concentrating, and drying.

The harmful substances comprise residual pesticides, harmful heavy metals, plasticizers and organic solvents. The pesticide comprises: quintozene, ethion, dimethoate, methamidophos, cypermethrin and fenvalerate. The harmful heavy metals include: lead, cadmium, mercury and chromium. The plasticizer comprises: di-n-butyl phthalate (DBP), di (. alpha. -ethyl) hexyl phthalate (DEHP), and diisononyl phthalate (DINP). The organic solvent comprises: ethanol and methanol.

The method for removing harmful substances in the momordica grosvenori extract provided by the invention comprises the steps of dissolving the momordica grosvenori extract, and carrying out enzymolysis to obtain an enzymolysis solution;

the fructus momordicae extract is an extract prepared by taking fructus momordicae as a raw material and performing leaching, solid-liquid separation, clarification, or further chromatographic separation and purification, or further decoloring and desalting, concentration and drying. Wherein, the content of the mogroside V which is an effective component of the grosvenor momordica extract is preferably 3.5 to 90 percent.

The present invention is not limited to the specific extraction method described above, and those skilled in the art will be familiar with the method.

The enzyme is organophosphorus degrading enzyme; the unit of enzyme activity is 1-20 ten thousand U/g.

The dissolving of the invention is to fully dissolve the grosvenor momordica fruit extract and enzyme in hot water and keep the temperature. The dissolution was also accompanied by continuous stirring and incubation. The temperature of the hot water is preferably 30-60 ℃. The heat preservation time is preferably 2-4 h.

Wherein the momordica grosvenori extract: enzyme: the mass ratio of water is preferably 1: 0.01-0.08: 25-40; more preferably 1: 0.02-0.07: 28 to 38.

Adding alkali into the solution after enzymolysis to adjust the pH value, and then adding a chelating agent for reaction. The chelation process described in the present invention is also accompanied by constant stirring and incubation. The heat preservation time is preferably 2-4 h.

Wherein the alkali is any one of sodium hydroxide or potassium hydroxide; the pH value is 8-10;

the chelating agent is preferably any one of EDTA or EDTA disodium; the adding mass of the chelating agent is preferably 0.5-1% of that of the fructus momordicae extract; more preferably 0.6% to 0.8%.

The inventors have creatively found that under alkaline conditions, the chelating (binding) strength and stability of the chelate complex can be further enhanced, thereby ensuring that the chelate complex is not dissociated and eluted by alcohol.

And concentrating and drying after reaction to obtain a dry product.

The concentration is to concentrate the liquid after the reaction until the solid content is 15-30%.

The concentration mode is to remove water, and includes but is not limited to one of falling film concentration, single-effect evaporation concentration or multiple-effect evaporation concentration.

The drying is for removing water, and includes but not includes any one of vacuum drying, forced air drying, vacuum microwave drying and vacuum freeze drying.

Eluting the dried product by using alkaline alcohol, and collecting the eluent; the method specifically comprises the following steps: placing the dried product in a chromatographic column, eluting by using alkaline alcohol, and collecting eluent; it may also be referred to as leaching it with a solvent and collecting the wash liquor. The leakage mode is either from bottom to top or from top to bottom.

The height ratio of the diameter of the chromatographic column is 1: 5-10; the flow rate of the column washing is 0.5-1 bv/h;

the alkaline alcohol is sodium ethoxide, potassium ethoxide, sodium methoxide or potassium methoxide; the volume fraction of the basic alcohol is more than 95%. The pH value of the alkaline alcohol is 8-10.

Wherein the mass ratio of the alkaline alcohol to the fructus momordicae extract is (6-10): 1.

the eluate is concentrated by evaporation. The concentration of the invention is to remove alcohols, and includes but is not limited to one of falling film concentration, single effect evaporation concentration or multiple effect evaporation concentration. Concentrating until no alcohol smell is obtained.

Concentrating, diluting, and purifying with macroporous adsorbent resin column.

The dilution is to dilute the concentrated solution to a solid matter by pure water, and the solid matter is preferably 4 to 10 percent; more preferably 5% to 9%.

The macroporous adsorption resin column is preferably any one of D101, AB-8, X-5, DM130, D101C, LX-100B, LX-T28 and LX-T81; the dosage of the macroporous adsorption resin is 17-25 times of the total amount of mogroside substances in the fructus momordicae extract.

The height ratio of the diameter of the macroporous adsorption resin column is 1: 3-7; the flow rate of the macroporous absorption resin column is 0.5 bv/h.

And then washing the column, desorbing, collecting the desorption solution, concentrating and drying to obtain the catalyst.

The column washing method specifically comprises the following steps: and (3) sequentially using an alkaline solvent, an acidic solvent and subcritical water to wash the column.

The volume of the alkaline solvent column is selected from 3-6 bv; the volume of the acid solvent column is selected from 3-6 bv; the volume of the subcritical water washing column is selected from 3-6 bv; the flow rate of the column washing is 1-2 bv/h.

Wherein the alkaline solvent is an alkaline aqueous solution containing a surfactant; the alkaline aqueous solution is preferably a sodium hydroxide aqueous solution with the mass fraction of 0.3-1%; more preferably an aqueous solution of sodium hydroxide with a mass fraction of 0.4% to 0.9%.

The acid solvent is an acid aqueous solution containing a surfactant; the acidic aqueous solution is preferably a hydrochloric acid aqueous solution with the mass fraction of 0.3-1%; more preferably 0.4 to 0.8% by mass.

The surfactant is ammonium phosphatide, propylene glycol fatty acid ester, propylene glycol alginate, succinic acid monoglyceride, polyglycerol ricinoleate, polyglycerol fatty acid ester, polyoxyethylene xylitol anhydride monostearate, polyoxyethylene sorbitan monolaurate (also named Tween, such as Tween 20, Tween 40, Tween 60 and Tween 80), xylitol anhydride monostearate, citric acid fatty glyceride, hydrogenated rosin glyceride, lactic acid fatty glyceride, sorbitan monolaurate (also named span 20), sorbitan monopalmitate (also named span 40), sorbitan monostearate (also named span 60), sorbitan tristearate (also named span 65), sorbitan monooleate (also named span 80), sucrose fatty acid ester, modified soybean phosphatide, enzymolysis soybean phosphatide, acetylation monoglyceride fatty acid ester, Acetylated diglycerol fatty acid ester; preference is given to diacetyl tartaric acid esters of mono-and diglycerides and/or acetylated monoglycerides.

The addition amount of the surfactant is preferably 0.01-0.1 wt%; more preferably 0.02 wt% to 0.08 wt%.

The subcritical water is pure water with the temperature of 130-200 ℃ and the pressure of 15-20 MPa; in the subcritical water column washing process, the temperature and pressure in the chromatographic column are kept consistent with subcritical water.

The desorption is carried out on the chromatographic column which is cooled and recovered to normal pressure by using alcohols as solvents. The desorbed solvent is an alcohol; the alcohol is ethanol or methanol; the volume fraction of the alcohols is 65-80%; the desorption flow rate is 0.5-1.5 bv/h; the using amount of the alcohols is 3-4 bv.

Concentrating the desorption solution, wherein the concentration is to concentrate the liquid after the reaction until the solid content is 15-30%; the concentration mode is to remove water, and includes but is not limited to one of falling film concentration, single-effect evaporation concentration or multiple-effect evaporation concentration.

The drying is specifically that after the negative pressure drying is carried out to constant weight, the drying is carried out to constant weight under normal pressure, and the steps are carried out alternately for 2-3 times.

The negative pressure drying is vacuum microwave drying or vacuum drying; the drying temperature is 140-160 ℃, and the vacuum degree is-0.07 to-0.1 MPa; the drying time is 1-2 h, and the drying time under normal pressure is 1-2 h.

The invention dissolves the grosvenor momordica fruit extract containing harmful substances in the water solution of organic phosphorus degrading enzyme, which can directly and primarily degrade organic phosphorus pesticide, then adjusts alkali and adds chelating agent to chelate heavy metal, thereby forming chelated heavy metal organic matter. Then concentrating and drying the extract, and washing the dried extract by utilizing the property that chelated heavy metal organic matters are insoluble in alcohols and mogroside dissolves alcohols, thereby realizing the effective removal of heavy metals. And then, removing alcohol from the washing liquid, feeding the washing liquid into a chromatographic column, adsorbing mogroside on the chromatographic column, washing the chromatographic column by adopting an alkaline and acidic aqueous solution containing a surfactant and subcritical water, effectively degrading and eluting residual pesticide and plasticizer, eluting residual heavy metal and chelated heavy metal organic matters, desorbing by using alcohols to obtain a desorption solution, concentrating the desorption solution, and repeatedly drying the desorption solution under the conditions of high temperature, negative pressure and normal pressure for a long time to remove an organic solvent to obtain the momordica grosvenori extract with harmful substances removed.

The invention provides a method for removing harmful substances in a grosvenor momordica extract, which comprises the following steps of A) dissolving the grosvenor momordica extract, and carrying out enzymolysis to obtain an enzymolysis solution; B) adding alkali into the solution after enzymolysis to adjust the pH value, adding a chelating agent for reaction, and concentrating and drying after reaction to obtain a dry product; C) eluting the dried product by using alkaline alcohol, and collecting the eluent; D) evaporating and concentrating the eluent, loading onto macroporous adsorbent resin column, eluting, desorbing, collecting desorption solution, concentrating, and drying. Through the process, the pesticide residue, heavy metal, organic solvent and plasticization can be simultaneously removed, and the process is simple and has strong industrialization capability.

In order to further illustrate the present invention, the following will describe the method for removing harmful substances from luo han guo extract in detail with reference to the following examples.

The starting materials or chemicals used in the examples of the present invention are, unless otherwise specified, commercially available in a conventional manner.

(1) The detection method of the pesticide residue comprises the following steps: pentachloronitrobenzene, ethion, dimethoate, methamidophos, cypermethrin and fenvalerate are detected according to 2341 pesticide residue determination method of the general rules of the four departments in 2020 edition of Chinese pharmacopoeia.

(2) The detection method of the heavy metal residue comprises the following steps: the content distribution of lead, cadmium, mercury and chromium is detected according to the first method of GB5009.12-2017, the first and second methods of GB 5009.15-2014 and GB 5009.17-2014 and the method specified in GB 5009.123-2014.

(3) The plasticizer residue detection method comprises the following steps: di-n-butyl phthalate (DBP), di (. alpha. -ethyl) hexyl phthalate (DEHP) and diisononyl phthalate (DINP) were measured according to the first and second methods, respectively, of phthalate in food safety national Standard GB 5009.271-2016.

(4) The detection method of the organic solvent residue comprises the following steps: the detection is carried out according to A.4 in the GB 8270-2014 food safety national standard food additive stevioside appendix A.

(5) The detection method of mogroside V comprises the following steps: the detection is carried out according to the determination method of the food additive mogroside of GB1886.77-2016 food safety national standard.

The momordica grosvenori extract used in the embodiment of the present invention is provided by rich bioengineering limited company in the west and the river, and the content of the stevioside V and harmful substances thereof is as follows.

Example 1

(1) Enzymolysis: 50g of fructus momordicae extract A (stevioside V25.9%) is dissolved in hot water with the temperature of 45 ℃ and the temperature of 30 times, 0.5g of organophosphorus degrading enzyme is added at the same time, and the temperature is kept for enzymolysis for 4 hours.

(2) Chelating: adjusting pH to 8 with sodium hydroxide, adding ETDA 1 wt% of fructus Siraitiae Grosvenorii extract A, and chelating for 4 hr.

(3) Drying and washing: and (3) performing single-effect evaporation concentration on the solution after the step (2) is finished, performing microwave drying to constant weight, and filling the dried product into a chromatographic column, wherein the diameter of the chromatographic column is 1: 10. Then, the column was washed with sodium hydroxide alkaline ethanol having a pH of 8 at an ethanol concentration of 95% at a flow rate of 0.5bv/h in an amount of 400ml, and all the washing solution was collected.

(4) Chromatography: and (3) evaporating and concentrating the washing liquid in a single-effect manner until no alcohol smell exists, diluting the washing liquid with pure water until the solid content is 4%, and then loading the diluted washing liquid into a D101 column with the diameter-height ratio of 1: and 5, the flow rate of the column feeding is 0.5BV/h, and after the column feeding is finished, the column is washed by using 5BV of alkaline aqueous solution (0.02 percent of Tween 20 and 0.3 percent of sodium hydroxide) with a surfactant, 5BV of acidic aqueous solution (0.02 percent of citric acid fatty glyceride and 0.3 percent of hydrochloric acid) with the surfactant and 5BV of subcritical water washing column (the temperature is 160 ℃ and the pressure is 15 MPa). Then desorbing by using 70 percent by volume of ethanol water solution, and collecting desorption liquid.

(5) And (3) drying: concentrating the desorption solution by single effect evaporation, drying at 150 deg.C under-0.1 MPa to constant weight, recovering normal pressure, drying for 1 hr, drying under-0.1 MPa for 1 hr, and sieving.

Through the inspection:

the weight of the obtained product is as follows: 28.53g of mogroside V43.20%, the yield is 95.17%, and the content is improved by 66.80%.

Pesticide residues: the content of the quintozene is less than the detection limit of 0.005mg/kg, the content of the ethion is less than the detection limit of 0.005mg/kg, the content of the dimethoate is less than the detection limit of 0.005mg/kg, the content of the methamidophos is less than the detection limit of 0.005mg/kg, the content of the cypermethrin is less than the detection limit of 0.025mg/kg, and the content of the fenvalerate is less than the detection limit of 0.025mg/kg, and the content is not detected.

Heavy metals: lead is less than the detection limit of 0.02mg/kg, cadmium is less than the detection limit of 0.001mg/kg, mercury is less than the detection limit of 0.002mg/kg, and chromium is less than the detection limit of 0.01mg/kg, and the lead and the cadmium are all lower than the detection limit and are not detected.

Organic solvent: ethanol and methanol, not detected.

Plasticizer: DBP is less than the detection limit of 0.3mg/kg, DEHP is less than the detection limit of 0.5mg/kg, DINP is less than the detection limit of 0.5mg/kg, and the DBP, the DEHP and the DINP are not detected.

Example 2

(1) Enzymolysis: 50g of the momordica grosvenori extract B (the stevioside V43.10%) is dissolved in 27 times of hot water at 45 ℃ while 0.7g of organophosphorus degrading enzyme is added, and the mixture is subjected to heat preservation and enzymolysis for 4 hours.

(2) Chelating: adjusting pH to 8 with sodium hydroxide, adding 0.8% of ETDA disodium, and chelating for 4 hr.

(3) Drying and washing: and (3) performing single-effect evaporation concentration on the solution after the step (2) is finished, performing microwave drying to constant weight, and filling the dried product into a chromatographic column, wherein the diameter of the chromatographic column is 1: 10. Then, the column was washed with sodium hydroxide alkaline ethanol having a pH of 9 at an ethanol concentration of 95% at a flow rate of 0.6bv/h in an amount of 400ml, and the whole amount of the washing solution was collected.

(4) Chromatography: and (3) evaporating and concentrating the washing liquid in a single-effect manner until no alcohol smell exists, diluting the washing liquid with pure water until the solid content is 4%, and then loading the diluted washing liquid into an AB-8 column with the diameter-height ratio of 1: and 5, the flow rate of the column feeding is 0.5BV/h, and after the column feeding is finished, the column is washed by using 5BV of alkaline aqueous solution (0.02 percent of Tween 20 and 0.3 percent of sodium hydroxide) with a surfactant, 5BV of acidic aqueous solution (0.02 percent of citric acid fatty glyceride and 0.3 percent of hydrochloric acid) with the surfactant and 5BV of subcritical water washing column (the temperature is 160 ℃ and the pressure is 15 MPa). Then desorbing by using 70 percent by volume of ethanol water solution, and collecting desorption liquid.

(5) And (3) drying: concentrating the desorption solution by single effect evaporation, drying at 160 deg.C under-0.1 MPa to constant weight, recovering normal pressure, drying for 1 hr, drying under-0.1 MPa for 1 hr, and sieving.

Through the inspection:

the weight of the obtained product is as follows: 35.63g of mogroside V58.20 percent, the yield is 96.23 percent, and the content is improved by 35.03 percent.

Pesticide residues: the content of the quintozene is less than the detection limit of 0.005mg/kg, the content of the ethion is less than the detection limit of 0.005mg/kg, the content of the dimethoate is less than the detection limit of 0.005mg/kg, the content of the methamidophos is less than the detection limit of 0.005mg/kg, the content of the cypermethrin is less than the detection limit of 0.025mg/kg, and the content of the fenvalerate is less than the detection limit of 0.025mg/kg, and the content is not detected.

Heavy metals: lead is less than the detection limit of 0.02mg/kg, cadmium is less than the detection limit of 0.001mg/kg, mercury is less than the detection limit of 0.002mg/kg, and chromium is less than the detection limit of 0.01mg/kg, and the lead and the cadmium are all lower than the detection limit and are not detected.

Organic solvent: ethanol and methanol, not detected.

Plasticizer: DBP is less than the detection limit of 0.3mg/kg, DEHP is less than the detection limit of 0.5mg/kg, DINP is less than the detection limit of 0.5mg/kg, and the DBP, the DEHP and the DINP are not detected.

Example 3

(1) Enzymolysis: 50g of momordica grosvenori extract C (stevioside V86.40%) is dissolved in hot water with the temperature of 45 ℃ and the temperature of 38 times, 0.8g of organophosphorus degrading enzyme is added at the same time, and the mixture is subjected to heat preservation and enzymolysis for 3 hours.

(2) Chelating: adjusting pH to 8 with sodium hydroxide, adding ETDA 0.6% of fructus Siraitiae Grosvenorii extract A, and chelating for 4 hr.

(3) Drying and washing: and (3) performing single-effect evaporation concentration on the solution after the step (2) is finished, performing microwave drying to constant weight, and filling the dried product into a chromatographic column, wherein the diameter of the chromatographic column is 1: 10. Then, the column was washed with potassium hydroxide alkaline ethanol having a pH of 8 at an ethanol concentration of 95% at a flow rate of 0.7bv/h in an amount of 400ml, and the whole amount of the washing solution was collected.

(4) Chromatography: and (3) evaporating and concentrating the washing liquid in a single-effect manner until no alcohol smell exists, diluting the washing liquid with pure water until the solid content is 4%, and then loading the diluted washing liquid into an X-5 column with the diameter-height ratio of 1: 6, the flow rate of the column is 0.5BV/h, and after the column feeding is finished, the column is washed by using 5BV of alkaline aqueous solution (0.02 percent of Tween 20 and 0.3 percent of sodium hydroxide) with a surfactant, 5BV of acidic aqueous solution (0.02 percent of citric acid fatty glyceride and 0.3 percent of hydrochloric acid) with the surfactant and 5BV of subcritical water washing column (the temperature is 180 ℃ and the pressure is 15 MPa). Then desorbing by using 70 percent by volume of ethanol water solution, and collecting desorption liquid.

(5) And (3) drying: concentrating the desorption solution by single effect evaporation, drying at 155 deg.C under-0.1 MPa to constant weight, recovering normal pressure, drying for 1.5 hr, drying under-0.1 MPa for 1 hr, and sieving.

Through the inspection:

the weight of the obtained product is as follows: 43.63g, mogroside V92.50%, yield 93.42%, content increased by 7.06%.

Pesticide residues: the content of the quintozene is less than the detection limit of 0.005mg/kg, the content of the ethion is less than the detection limit of 0.005mg/kg, the content of the dimethoate is less than the detection limit of 0.005mg/kg, the content of the methamidophos is less than the detection limit of 0.005mg/kg, the content of the cypermethrin is less than the detection limit of 0.025mg/kg, and the content of the fenvalerate is less than the detection limit of 0.025mg/kg, and the content is not detected.

Heavy metals: lead is less than the detection limit of 0.02mg/kg, cadmium is less than the detection limit of 0.001mg/kg, mercury is less than the detection limit of 0.002mg/kg, and chromium is less than the detection limit of 0.01mg/kg, and the lead and the cadmium are all lower than the detection limit and are not detected.

Organic solvent: ethanol and methanol, not detected.

Plasticizer: DBP is less than the detection limit of 0.3mg/kg, DEHP is less than the detection limit of 0.5mg/kg, DINP is less than the detection limit of 0.5mg/kg, and the DBP, the DEHP and the DINP are not detected.

Comparative example 1

(1) Enzymolysis: 50g of fructus momordicae extract A (stevioside V25.9%) is dissolved in hot water with the temperature of 45 ℃ and the temperature of 30 times, 0.5g of organophosphorus degrading enzyme is added at the same time, and the temperature is kept for enzymolysis for 4 hours.

(2) Chelating: adding ETDA into the solution after enzymolysis, wherein the addition amount of ETDA is 1% of the weight of the fructus Siraitiae Grosvenorii extract A, and continuously chelating for 4 h.

(3) Drying and washing: and (3) performing single-effect evaporation concentration on the solution after the step (2) is finished, performing microwave drying to constant weight, and filling the dried product into a chromatographic column, wherein the diameter of the chromatographic column is 1: 10. Then, the column was washed with sodium hydroxide alkaline ethanol having a pH of 8 at an ethanol concentration of 95% at a flow rate of 0.5bv/h in an amount of 400ml, and all the washing solution was collected.

(4) Chromatography: and (3) evaporating and concentrating the washing liquid in a single-effect manner until no alcohol smell exists, diluting the washing liquid with pure water until the solid content is 4%, and then loading the diluted washing liquid into a D101 column with the diameter-height ratio of 1: and 5, the flow rate of the column feeding is 0.5BV/h, and after the column feeding is finished, the column is washed by using 5BV of alkaline aqueous solution (0.02 percent of Tween 20 and 0.3 percent of sodium hydroxide) with a surfactant, 5BV of acidic aqueous solution (0.02 percent of citric acid fatty glyceride and 0.3 percent of hydrochloric acid) with the surfactant and 5BV of subcritical water washing column (the temperature is 160 ℃ and the pressure is 15 MPa). Then desorbing by using 70 percent by volume of ethanol water solution, and collecting desorption liquid.

(5) And (3) drying: concentrating the desorption solution by single effect evaporation, drying at 150 deg.C under-0.1 MPa to constant weight, recovering normal pressure, drying for 1 hr, drying under-0.1 MPa for 1 hr, and sieving.

Through the inspection:

the weight of the obtained product is as follows: 28.31g of mogroside V43.04 percent, the yield is 94.08 percent, and the content is improved by 66.18 percent.

Pesticide residues: the content of the quintozene is less than the detection limit of 0.005mg/kg, the content of the ethion is less than the detection limit of 0.005mg/kg, the content of the dimethoate is less than the detection limit of 0.005mg/kg, the content of the methamidophos is less than the detection limit of 0.005mg/kg, the content of the cypermethrin is less than the detection limit of 0.025mg/kg, and the content of the fenvalerate is less than the detection limit of 0.025mg/kg, and the content is not detected.

Heavy metals: lead 0.04mg/kg is more than the detection limit 0.02mg/kg, cadmium 0.042mg/kg is more than the detection limit 0.001mg/kg, mercury is less than the detection limit 0.002mg/kg, and chromium is less than the detection limit 0.01 mg/kg. Namely: lead and cadmium are not removed completely; and mercury and chromium are both below the detection limit and are not detected. Heavy metals remain.

Organic solvent: ethanol and methanol, not detected.

Plasticizer: DBP is less than the detection limit of 0.3mg/kg, DEHP is less than the detection limit of 0.5mg/kg, DINP is less than the detection limit of 0.5mg/kg, and the DBP, the DEHP and the DINP are not detected.

Comparative example 2

(1) Enzymolysis: 50g of fructus momordicae extract A (stevioside V25.9%) is dissolved in hot water with the temperature of 45 ℃ and the temperature of 30 times, 0.5g of organophosphorus degrading enzyme is added at the same time, and the temperature is kept for enzymolysis for 4 hours.

(2) Chelating: adjusting pH to 8 with sodium hydroxide, adding ETDA 1 wt% of fructus Siraitiae Grosvenorii extract A, and chelating for 4 hr.

(3) Drying and washing: and (3) performing single-effect evaporation concentration on the solution after the step (2) is finished, performing microwave drying to constant weight, and filling the dried product into a chromatographic column, wherein the diameter of the chromatographic column is 1: 10. The column was then washed with pure water to collect the entire washing solution.

And (4) washing to obtain pure water in the step (3).

(4) Chromatography: and (3) evaporating and concentrating the washing liquid in a single-effect manner until no alcohol smell exists, diluting the washing liquid with pure water until the solid content is 4%, and then loading the diluted washing liquid into a D101 column with the diameter-height ratio of 1: and 5, the flow rate of the column feeding is 0.5BV/h, and after the column feeding is finished, the column is washed by using 5BV of alkaline aqueous solution (0.02 percent of Tween 20 and 0.3 percent of sodium hydroxide) with a surfactant, 5BV of acidic aqueous solution (0.02 percent of citric acid fatty glyceride and 0.3 percent of hydrochloric acid) with the surfactant and 5BV of subcritical water washing column (the temperature is 160 ℃ and the pressure is 15 MPa). Then desorbing by using 70 percent by volume of ethanol water solution, and collecting desorption liquid.

(5) And (3) drying: concentrating the desorption solution by single effect evaporation, drying at 150 deg.C under-0.1 MPa to constant weight, recovering normal pressure, drying for 1 hr, drying under-0.1 MPa for 1 hr, and sieving.

Through the inspection:

the weight of the obtained product is as follows: 27.67g, mogroside V42.89%, yield 91.64%, content improved 65.60%.

Pesticide residues: the content of the quintozene is less than the detection limit of 0.005mg/kg, the content of the ethion is less than the detection limit of 0.005mg/kg, the content of the dimethoate is less than the detection limit of 0.005mg/kg, the content of the methamidophos is less than the detection limit of 0.005mg/kg, the content of the cypermethrin is less than the detection limit of 0.025mg/kg, and the content of the fenvalerate is less than the detection limit of 0.025mg/kg, and the content is not detected.

Heavy metals: lead 0.03mg/kg > detection limit 0.02mg/kg, cadmium 0.082mg/kg > detection limit 0.001mg/kg, mercury < detection limit 0.002mg/kg and chromium 0.04 > detection limit 0.01 mg/kg. Namely: lead, cadmium and chromium are not removed completely; and mercury is lower than the detection limit and is not detected.

Organic solvent: ethanol and methanol, not detected.

Plasticizer: DBP is less than the detection limit of 0.3mg/kg, DEHP is less than the detection limit of 0.5mg/kg, DINP is less than the detection limit of 0.5mg/kg, and the DBP, the DEHP and the DINP are not detected.

Comparative example 3

(1) Enzymolysis: 50g of fructus momordicae extract A (stevioside V25.9%) is dissolved in hot water with the temperature of 45 ℃ and the temperature of 30 times, 0.5g of organophosphorus degrading enzyme is added at the same time, and the temperature is kept for enzymolysis for 4 hours.

(2) Chelating: adjusting pH to 8 with sodium hydroxide, adding ETDA 1 wt% of fructus Siraitiae Grosvenorii extract A, and chelating for 4 hr.

(3) Drying and washing: and (3) performing single-effect evaporation concentration on the solution after the step (2) is finished, performing microwave drying to constant weight, and filling the dried product into a chromatographic column, wherein the diameter of the chromatographic column is 1: 10. Then, the column was washed with sodium hydroxide alkaline ethanol having a pH of 8 at an ethanol concentration of 95% at a flow rate of 0.5bv/h in an amount of 400ml, and all the washing solution was collected.

(4) Chromatography: and (3) evaporating and concentrating the washing liquid in a single-effect manner until no alcohol smell exists, diluting the washing liquid with pure water until the solid content is 4%, and then loading the diluted washing liquid into a D101 column with the diameter-height ratio of 1: and 5, the flow rate of the column feeding is 0.5BV/h, and after the column feeding is finished, the column is washed by using 5BV of an alkaline aqueous solution (0.02 percent of Tween 20) with a surfactant, 5BV of a neutral aqueous solution (0.02 percent of citric acid fatty glyceride) with the surfactant and 5BV of a subcritical water washing column (the temperature is 160 ℃ and the pressure is 15MPa) in sequence. Then desorbing by using 70 percent by volume of ethanol water solution, and collecting desorption liquid.

(5) And (3) drying: concentrating the desorption solution by single effect evaporation, drying at 150 deg.C under-0.1 MPa to constant weight, recovering normal pressure, drying for 1 hr, drying under-0.1 MPa for 1 hr, and sieving.

Through the inspection:

the weight of the obtained product is as follows: 31.12g of mogroside V40.18 percent, the yield is 96.55 percent, and the content is improved by 55.14 percent.

Pesticide residues: 0.011mg/kg of quintozene is more than the detection limit of 0.005mg/kg, ethion is less than the detection limit of 0.005mg/kg, dimethoate is less than the detection limit of 0.005mg/kg, methamidophos is 0.008mg/kg is more than the detection limit of 0.005mg/kg, cypermethrin is 0.030mg/kg is more than the detection limit of 0.025mg/kg, and fenvalerate is 0.030mg/kg is more than the detection limit of 0.025 mg/kg. Namely: the quintozene, the methamidophos, the cypermethrin and the fenvalerate are not removed completely; the others are all below the detection limit and are not detected.

Heavy metals: lead is less than the detection limit of 0.02mg/kg, cadmium is 0.085mg/kg is more than the detection limit of 0.001mg/kg, mercury is less than the detection limit of 0.002mg/kg, and chromium is less than the detection limit of 0.01 mg/kg. Namely: the cadmium is not removed completely; lead, mercury and chromium are all below the detection limit and are not detected.

Organic solvent: ethanol and methanol, not detected.

Plasticizer: DBP0.83mg/kg is more than the detection limit of 0.3mg/kg, DEHP1.91mg/kg is more than the detection limit of 0.5mg/kg, and DINP is less than the detection limit of 0.5 mg/kg. Namely: DBP and DEHP were not removed, NINP was below detection limit and was not detected.

The result is that pesticide residues, heavy metals and their plasticizers are not removed cleanly.

Comparative example 4

(1) Enzymolysis: 50g of fructus momordicae extract A (stevioside V25.9%) is dissolved in hot water with the temperature of 45 ℃ and the temperature of 30 times, 0.5g of organophosphorus degrading enzyme is added at the same time, and the temperature is kept for enzymolysis for 4 hours.

(2) Chelating: adjusting pH to 8 with sodium hydroxide, adding ETDA 1 wt% of fructus Siraitiae Grosvenorii extract A, and chelating for 4 hr.

(3) Drying and washing: and (3) performing single-effect evaporation concentration on the solution after the step (2) is finished, performing microwave drying to constant weight, and filling the dried product into a chromatographic column, wherein the diameter of the chromatographic column is 1: 10. Then, the column was washed with sodium hydroxide alkaline ethanol having a pH of 8 at an ethanol concentration of 95% at a flow rate of 0.5bv/h in an amount of 400ml, and all the washing solution was collected.

(4) Chromatography: and (3) evaporating and concentrating the washing liquid in a single-effect manner until no alcohol smell exists, diluting the washing liquid with pure water until the solid content is 4%, and then loading the diluted washing liquid into a D101 column with the diameter-height ratio of 1: and 5, the flow rate of the column feeding is 0.5BV/h, and after the column feeding is finished, the column is washed by using 5BV of alkaline aqueous solution (0.02 percent of Tween 20 and 0.3 percent of sodium hydroxide) with a surfactant, 5BV of acidic aqueous solution (0.02 percent of citric acid fatty glyceride and 0.3 percent of hydrochloric acid) with the surfactant and 5BV of subcritical water washing column (the temperature is 160 ℃ and the pressure is 15 MPa). Then desorbing by using 70 percent by volume of ethanol water solution, and collecting desorption liquid.

(5) And (3) drying: concentrating the desorption solution by single effect evaporation, drying at 150 deg.C under-0.1 MPa to constant weight, and sieving.

Through the inspection:

the weight of the obtained product is as follows: 28.04g, mogroside V44.40%, yield 96.14%, content increased by 71.43%.

Pesticide residues: the content of the quintozene is less than the detection limit of 0.005mg/kg, the content of the ethion is less than the detection limit of 0.005mg/kg, the content of the dimethoate is less than the detection limit of 0.005mg/kg, the content of the methamidophos is less than the detection limit of 0.005mg/kg, the content of the cypermethrin is less than the detection limit of 0.025mg/kg, and the content of the fenvalerate is less than the detection limit of 0.025mg/kg, and the content is not detected.

Heavy metals: lead is less than the detection limit of 0.02mg/kg, cadmium is less than the detection limit of 0.001mg/kg, mercury is less than the detection limit of 0.002mg/kg, and chromium is less than the detection limit of 0.01mg/kg, and the lead and the cadmium are all lower than the detection limit and are not detected.

Organic solvent: ethanol 46.2mg/kg, methanol was not detected. I.e. the ethanol is not removed completely.

Plasticizer: DBP is less than the detection limit of 0.3mg/kg, DEHP is less than the detection limit of 0.5mg/kg, DINP is less than the detection limit of 0.5mg/kg, and the DBP, the DEHP and the DINP are not detected.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (11)

1. A method for removing harmful substances from fructus Siraitiae Grosvenorii extract comprises:

A) dissolving fructus Siraitiae Grosvenorii extract, and performing enzymolysis to obtain solution after enzymolysis;

B) adding alkali into the solution after enzymolysis to adjust the pH value, adding a chelating agent for reaction, and concentrating and drying after reaction to obtain a dry product;

C) eluting the dried product by using alkaline alcohol, and collecting the eluent;

D) evaporating and concentrating the eluent, loading onto macroporous adsorbent resin column, eluting, desorbing, collecting desorption solution, concentrating, and drying.

2. The method of claim 1, wherein the mogroside V content of the Luo Han Guo extract of step A) is from 3.5% to 90%.

3. The method of claim 1, wherein the enzyme of step a) is an organophosphate degrading enzyme; the unit of enzyme activity is 1-20 ten thousand U/g; the fructus momordicae extract: enzyme: the mass ratio of water is 1: 0.01-0.08: 25-40;

the dissolving is carried out by adding water, and the dissolving temperature is 30-60 ℃.

4. The method of claim 1, wherein the chelating agent of step B) is any one of EDTA or disodium EDTA; the added mass of the chelating agent is 0.5-1% of that of the grosvenor momordica extract.

5. The method according to claim 1, wherein the alkali in step B) is any one of sodium hydroxide or potassium hydroxide; the pH value is 8-10;

the concentration is carried out until the solid content is 15 to 30 percent.

6. The process according to claim 1, wherein the basic alcohol of step C) is sodium ethoxide, potassium ethoxide, sodium methoxide or potassium methoxide; the mass ratio of the alkaline alcohol to the fructus momordicae extract is (6-10): 1; the volume fraction of the basic alcohol is more than 95%.

7. The method according to claim 1, wherein step C) is in particular: placing the dried product in a chromatographic column, eluting by using alkaline alcohol, and collecting eluent; the height ratio of the chromatographic column diameter is 1: 5-10; the flow rate of the column washing is 0.5-1 bv/h.

8. The method of claim 1, wherein the macroporous adsorbent resin column of step D) is any one of D101, AB-8, X-5, DM130, D101C, LX-100B, LX-T28, LX-T81;

the height ratio of the diameter of the macroporous adsorption resin column is 1: 3-7; the flow rate of the macroporous absorption resin column is 0.5 bv/h.

9. The method according to claim 1, wherein the step D) of washing the column is specifically: sequentially using an alkaline solvent, an acidic solvent and subcritical water to wash the column; the volumes of the alkaline solvent, the acidic solvent and the subcritical water washing column are independently selected from 3-6 bv; the flow rate of the column washing is 1-2 bv/h.

10. The method according to claim 9, wherein the alkaline solvent is an alkaline aqueous solution containing a surfactant; the alkaline aqueous solution is a sodium hydroxide aqueous solution with the mass fraction of 0.3-1%;

the acid solvent is an acid aqueous solution containing a surfactant; the acidic aqueous solution is 0.3-1% of hydrochloric acid aqueous solution by mass;

the surfactant is ammonium phosphatide, propylene glycol fatty acid ester, propylene glycol alginate, succinic acid monoglyceride, polyglycerol ricinoleate, polyglycerol fatty acid ester, polyoxyethylene xylitol anhydride monostearate, polyoxyethylene sorbitan monolaurate, xylitol anhydride monostearate, citric acid fatty glyceride, hydrogenated rosin glyceride, lactic acid fatty glyceride, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sucrose fatty acid ester, modified soybean phosphatide, enzymolysis soybean phosphatide, acetylation monoglyceride fatty acid ester, acetylation diglycerol fatty acid ester; preferably diacetyl tartaric acid ester of mono-di-glycerides and/or acetylated mono-glycerides fatty acids;

the addition amount of the surfactant is 0.01-0.1 wt%;

the subcritical water is pure water with the temperature of 130-200 ℃ and the pressure of 15-20 MPa.

11. The method of claim 1, wherein the desorbed solvent of step D) is an alcohol; the alcohol is ethanol or methanol; the volume fraction of the alcohols is 65-80%; the desorption flow rate is 0.5-1.5 bv/h; the using amount of the alcohols is 3-4 bv;

the drying is specifically that after the negative pressure drying is carried out to constant weight, the drying is carried out to constant weight under normal pressure, and the steps are alternated for 2-3 times;

the negative pressure drying is vacuum microwave drying or vacuum drying; the drying temperature is 140-160 ℃, and the vacuum degree is-0.07 to-0.1 MPa; the drying time is 1-2 h, and the drying time under normal pressure is 1-2 h.