CN116941765A - Improved co-production method of pesticide residue-free momordica grosvenori sweet glycoside composition - Google Patents
Improved co-production method of pesticide residue-free momordica grosvenori sweet glycoside composition Download PDFInfo
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- CN116941765A CN116941765A CN202310939346.7A CN202310939346A CN116941765A CN 116941765 A CN116941765 A CN 116941765A CN 202310939346 A CN202310939346 A CN 202310939346A CN 116941765 A CN116941765 A CN 116941765A
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- water
- activated carbon
- ethanol
- extract
- momordica grosvenori
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J17/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, having an oxygen-containing hetero ring not condensed with the cyclopenta(a)hydrophenanthrene skeleton
- C07J17/005—Glycosides
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/105—Plant extracts, their artificial duplicates or their derivatives
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
- A23L5/27—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
- A23L5/27—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption
- A23L5/273—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption using adsorption or absorption agents, resins, synthetic polymers, or ion exchangers
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
- A23L5/27—Removal of unwanted matter, e.g. deodorisation or detoxification by chemical treatment, by adsorption or by absorption
- A23L5/276—Treatment with inorganic compounds
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Botany (AREA)
- Mycology (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to an improved co-production method of a pesticide residue-free momordica grosvenori sweet glycoside composition, which comprises the steps of soaking momordica grosvenori in hot water containing a slow-release oxidant to complete fixation, pulping and extracting, countercurrent extraction, horizontal screw centrifugation, disc centrifugation, ceramic membrane filtration, sterilization, macroporous resin adsorption, resin column impurity removal by sequentially flushing dilute alkali liquor and water, gradient elution I by using medium ethanol, gradient elution II by using high ethanol aqueous solution, and adding eluent into modified activated carbon. The extract prepared by the method has no pesticide residue, and the mogroside has high yield, thus being a high-quality momordica grosvenori extract. The preparation method of the momordica grosvenori extract is simple in process equipment requirement, can be operated continuously and is suitable for industrialization.
Description
Technical Field
The invention relates to an extraction method of momordica grosvenori, in particular to an improved co-production method of a pesticide residue-free momordica grosvenori sweet glycoside composition.
Background
The mogroside is a main component in the fructus momordicae extract, is a sweetener which is basically nontoxic, safe to take, high in sweetness, almost free of heat, free of influencing the blood sugar content of normal people, safe and healthy. Because of its many excellent properties, mogrosides can replace sucrose in whole or in part, and thus find wide application in the food industry. In addition, the mogrosides also have very broad application prospect and market potential in the fields of medicines, cosmetics and health foods.
Consumption of mogrosides is concentrated in the united states, europe, japan, and the like. Currently, the united states is the largest consumer country for mogrosides. Fructus momordicae extract yield and demand steadily increase since the us FDA admitted fructus momordicae glycoside to the market in 2010 as a general sweetener, and us consumers also have a positive attitude towards fructus momordicae extract. From 2011 to date, the number of new food and beverage releases containing momordica grosvenori extracts worldwide is increasing. In addition, the use of sugar substitutes containing momordica grosvenori extracts in food and beverage has been spread over various fields. Along with the increasing growth of the market of the momordica grosvenori extract, the international high-end food brand has higher requirements on the quality of the momordica grosvenori extract, the European Union and the United states continuously revise pesticide residue standards, and particularly the European Union greatly improves the pesticide residue standards, and in order to ensure that the momordica grosvenori extract has competitiveness in the international market, one important index is pesticide residue. The domestic production enterprises which have the capability of producing the Siraitia grosvenorii extract without pesticide residues accord with European Union and United states pharmacopoeia standards.
In the prior art, the technology for reducing pesticide residues and even the momordica grosvenori extract without pesticide residues is summarized as follows:
CN201410657496.X discloses a method for reducing carbendazim in fructus Siraitiae Grosvenorii extract, which comprises the steps of dissolving fructus Siraitiae Grosvenorii extract in deionized water, adjusting acid, treating with active carbon column, adjusting alkali, nanofiltration, concentrating, drying, etc., to obtain fructus Siraitiae Grosvenorii extract with carbendazim content lower than 0.01 mg/kg. The method has the advantages that excessive use of activated carbon tends to cause loss of mogroside, low yield of unit mass of fructus momordicae, and no cost advantage; in addition, the method only has the effect of partially removing pesticide residues of carbendazim, and does not show whether pesticide residues of other types are effective or not.
CN201680034301.3 discloses a pesticide-free momordica grosvenori extract and a preparation method thereof, wherein the momordica grosvenori extract is taken as a raw material, and is obtained through the steps of dissolution, active carbon column treatment, ethanol elution, reduced pressure concentration, drying and the like. The method has the defects of single means for removing pesticide residues and larger loss of the stevioside.
CN202111362720.9 discloses a method for removing harmful substances from fructus momordicae extract, which takes fructus momordicae extract as raw material, and obtains the fructus momordicae extract for removing pesticide residues, heavy metals and plasticizers through the steps of dissolving, enzymolysis, alkali adjustment, chelation reaction, concentration, drying, alkaline alcohol elution, concentration, macroporous resin adsorption, desorption, concentration, drying and the like. The method has the advantages of redundant steps, small treatment capacity and high production cost, and is not suitable for industrial production.
CN202210409676.0 discloses a method for producing momordica grosvenori sweet glycoside for removing pesticide residue on a large scale, which uses dried momordica grosvenori fruit as raw material, and comprises the steps of hot water extraction, ultrafiltration, anion exchange resin column treatment, macroporous resin adsorption, degradation agent I, degradation agent II, hydrogen peroxide water solution column washing, ethanol analysis, concentration, drying and the like, thus obtaining the momordica grosvenori sweet glycoside for removing pesticide residue. The method has complicated steps, the mogroside is partially eluted in the process of washing the column for multiple times by multiple solutions, and the cost of the raw materials of the dried fructus momordicae is high, so that the method is not suitable for industrial continuous production.
CN201710388435.1 discloses a method for extracting both mogroside without pesticide residue and water-soluble dietary fiber, which is characterized in that the luo han guo is cleaned, boiled, chromatographed, ultrafiltered, nanofiltration and concentrated to obtain the luo han guo stevioside without pesticide residue. The method comprises the steps of removing fat-soluble pesticide residues through an alumina chromatographic column, and removing water-soluble pesticide residues through an activated carbon chromatographic column. But pesticide residues are not thoroughly removed.
CN2015141887. X discloses a method for removing pesticide residues from fructus Siraitiae Grosvenorii extract, which comprises treating activated carbon with alkali and acid, purifying fructus Siraitiae Grosvenorii extract aqueous solution with activated carbon chromatographic column, eluting, nanofiltration, vacuum concentrating, and spray drying to obtain extract with carbendazim content lower than 0.01 mg/kg.
Therefore, most of pesticide residue removal on momordica grosvenori in the prior art mainly focuses on using activity for adsorption, but the activated carbon adsorption can only carry out adsorption on limited pesticide residues, and the method has no universality. And a large amount of active carbon is adopted for adsorption, so that the yield of the effective component mogroside, especially the mogroside V with the main sweet taste effect is reduced.
The inventor of the prior patent CN202310284713.4 describes an industrial production method of the Siraitia grosvenorii extract without pesticide residues, which adopts hydrogen peroxide and alkali to deactivate green of the fresh Siraitia grosvenorii under the condition of hot water, and is favorable for removing pesticide residues on the surface of the Siraitia grosvenorii by utilizing the oxidation of the hydrogen peroxide and the alkaline condition. However, hydrogen peroxide is easily decomposed under heating, and the oxidizing property gradually decreases. And through a large number of experiments, the organic phosphorus pesticide residue removing effect is limited (methamidophos, omethoate, dimethoate, phorate, diazinon, parathion, methyl parathion, malathion, fenphos, quinalphos, inner phosphorus and trichlorfon). The main organic phosphorus is relatively chemically stable and is not easy to be removed by oxidation.
Therefore, research and development of an extraction technology and a preparation technology capable of thoroughly removing the pesticide residues in the fructus momordicae and developing high-quality fructus momordicae products have important practical significance.
Disclosure of Invention
The invention aims to solve the technical problems of incomplete pesticide residue removal, in particular to the incomplete removal of organophosphorus pesticide residues in the prior art, and provides a technology for extracting fructus momordicae which can realize industrialized production and thoroughly remove pesticide residues in the interior.
The technical scheme adopted for solving the technical problems is as follows:
an improved co-production method of a pesticide residue-free momordica grosvenori sweet glycoside composition comprises the following steps:
(1) Fresh fruit de-enzyming: soaking the whole fresh fructus Siraitiae Grosvenorii in hot water containing slow release oxidant, completely immersing, and taking out to obtain de-enzymed fresh fructus Siraitiae Grosvenorii; the slow-release oxidant is obtained by compounding polyvinyl alcohol and polyhydroxy fatty acid encapsulated superfine calcium peroxide;
(2) Pulping and extracting: adding the de-enzymed fresh fruits into a beating machine, and simultaneously, introducing hot water, and beating and extracting to obtain beating extract; collecting the extracted slag for later use;
(3) Countercurrent extraction: countercurrent extraction is carried out on the pulped extraction residues to obtain countercurrent extraction liquid;
(4) Horizontal screw centrifugation: mixing the beating extract and the countercurrent extract, and filtering with a horizontal decanter centrifuge to obtain horizontal decanter centrifuge filtrate;
(5) Disc centrifugation: filtering the horizontal spiral centrifugal filtrate by a disc type centrifugal machine to obtain disc type centrifugal filtrate;
(6) And (3) ceramic membrane filtration: filtering the disc-type centrifugal filtrate by using a ceramic membrane to obtain ceramic membrane filtrate;
(7) And (3) sterilization: sterilizing the ceramic membrane filtrate by UHT equipment, and cooling to obtain sterilized materials;
(8) Macroporous resin adsorption: passing the sterilized material through a macroporous adsorption resin column;
(9) Removing impurities: after the macroporous resin adsorption is finished, washing the resin column with dilute alkali liquor, and washing the resin column with pure water until the resin column is neutral;
(10) Gradient elution I: eluting with a macroporous adsorbent resin column with a moderate ethanol aqueous solution, adding modified activated carbon into the moderate ethanol eluent, heating, stirring, filtering, concentrating and drying to obtain a first fructus Siraitiae Grosvenorii extract;
(11) Gradient elution II: eluting with high ethanol water solution, adding modified activated carbon into the high ethanol eluate, heating, stirring, filtering, concentrating, and drying to obtain second fructus Siraitiae Grosvenorii extract;
the modified activated carbon is obtained by water washing activated carbon after activated carbon is activated at high temperature by an activating agent, wherein the activating agent comprises KOH and potassium permanganate.
Preferably, the slow release oxidizing agent is obtained by a preparation method comprising the steps of: and (3) dissolving polyvinyl alcohol and polyhydroxy fatty acid in an alcohol water solution, adding superfine calcium peroxide under the condition of ultrasonic stirring, dispersing uniformly, and freeze-drying the dispersion liquid to obtain the slow-release oxidant.
Further, the mass ratio of the polyvinyl alcohol to the polyhydroxy fatty acid to the alcohol aqueous solution to the superfine calcium peroxide is 20-30:5-8:100-160:10-15 parts; the volume concentration of alcohol in the alcohol water solution is 40-70vol%, and the alcohol is at least one selected from methanol, ethanol, propanol and ethylene glycol, preferably ethanol. Methanol is not used as much as possible in view of toxicity, but methanol is also capable of completing the present invention and should not be excluded from the essential content of the present invention.
Further, the particle size of the superfine calcium peroxide is 50-200nm; the preparation method of the superfine calcium peroxide comprises the following steps: dissolving calcium chloride in an alcohol water solution, filtering, adding a surfactant and ammonia water into the filtrate, slowly dropwise adding hydrogen peroxide under the stirring condition, dropwise adding NaOH/KOH solution to generate white precipitate, filtering, washing, and performing vacuum freeze drying to obtain the nano calcium peroxide.
Further, the molar ratio of the calcium chloride to the hydrogen peroxide is 3-5:1, and the mass concentration of the hydrogen peroxide is 20-35wt%; the surfactant is PEG with the number average molecular weight of 1000-2000, and the adding amount of the surfactant is 3-6wt% of the mass of the calcium chloride; the mass concentration of the ammonia water is 20-30%, and the pH value of the system is adjusted to 9-10 by adding the ammonia water; slowly dropwise adding hydrogen peroxide within 1-2h; the mass concentration of NaOH/KOH solution is 1-5wt%, and the addition amount makes the pH of the system 11-12; the alcohol aqueous solution is obtained by mixing ethanol and deionized water, wherein the volume content of the ethanol is 30-50%.
The prepared calcium peroxide is nano-scale superfine calcium peroxide, can be better embedded by a polymer, and has better slow release effect.
Further, the ultrasonic stirring condition is stirring at 30-60kHz and 600-1000 rpm; the freeze drying is that the dispersion is freeze dried for 5-10 hours at the temperature of-60 ℃ to-30 ℃ and the pressure of 10-100 Pa.
Preferably, in the step (1), the temperature of the hot water is 50-60 ℃, the dosage of the hot water is not particularly limited, the momordica grosvenori can be completely immersed, and the immersing time is 3-6 hours; the mass concentration of the slow-release oxidant is 2-3wt%. The process of the present invention employs a slow release oxidizing agent, reduces the hot water temperature and prolongs the soaking time relative to the inventors' prior patent 202310284713.4. Thus, although the whole process flow time is prolonged, the oxidation effect is better and thorough, and the removal effect on pesticide residues, especially organophosphorus pesticide residues, is better.
In the invention, the step (1) is to remove pesticide residues on complete fructus momordicae while deactivating enzymes, so that the internal components of the fructus momordicae (especially mogrosides) are not contacted with an oxidant and alkali, the loss of the mogrosides is avoided, and the diffusion and infiltration of trace oxidation products into the fructus momordicae are prevented. The slow-release oxidant slowly releases the oxidizing component in hot water and produces Ca (OH) 2 The system is made to be slightly alkaline, and is also beneficial to removing pesticide residues on the surface of the momordica grosvenori. No inorganic base is added. The purpose of deactivating the green of the fresh fructus momordicae is to deactivate various biological enzymes and proteins of the fructus momordicae and prevent browning caused by Maillard reaction, thereby ensuring light color of the extracting solution, the filtrate and the concentrated solution in each subsequent step; the second purpose of fixation is to kill various endophytic fungi and other microorganisms carried by the fresh fructus momordicae, and enzymes produced by the microorganisms are likely to have negative effects on the degradation of mogroside; the third purpose of the de-enzyming is that the alkaline aqueous solution can leach out flavonoid compounds, phenolic acids, oils and most pigments and pesticide residues in the shells of the fresh fruits of the momordica grosvenori, so that most impurities and pesticide residues are removed, the quality of materials in the subsequent steps is indirectly improved, and the quality of materials in the subsequent steps is reducedThe difficulty of separation and purification improves the quality and taste of the product.
Preferably, in step (2), the superheated water has a temperature of 102-115 ℃, preferably 105-110 ℃. The temperature of the superheated water is not easily too high, otherwise it is unstable. The dosage of the superheated water is 1-1.5 times of the weight of the fresh fructus momordicae, and the superheated water is generally extracted by warm water, 10-20 times of the superheated water is needed, and the superheated water is extracted for a plurality of times to achieve satisfactory yield. The high-temperature and high-pressure superheated water generated by the secondary heating mode is conveyed into the pulping machine under the traction of the pressure-resistant pipeline. Under the action of a pressure reducing valve arranged in the pressure-resistant pipeline, the flow and the flow speed of the superheated water can be regulated. When superheated water is poured from the shower head at the end of the pressure-resistant pipe, the pressure is rapidly released, accompanied by intense mass and heat transfer processes. The inventor finds that the extraction efficiency of the process is better than that of the common normal-pressure hot water beating extraction process with any temperature (normal temperature to 100 ℃), water resources are greatly saved, and the treatment cost of the extracted wastewater is reduced.
No report is made before the siraitia grosvenorii is pulped by using superheated water, and the inventor discovers that the advantage of pulping by using the superheated water in the siraitia grosvenorii extraction process is as follows: firstly, saving water and ensuring that most of mogrosides are leached out; secondly, the extraction process is finished in a large quantity and rapidly, so that the production efficiency is improved; and thirdly, the pollution of external microorganisms is prevented, and the degradation of mogroside is avoided.
Preferably, in the step (3), the water content of the countercurrent extraction is 1.5-3 times of the weight of the fresh fructus momordicae, and the extraction temperature is 85-95 ℃. The purpose of countercurrent extraction is to thoroughly leach the residual mogroside in the pulped extraction slag, so as to improve the total yield of the mogroside.
And (4) a horizontal decanter centrifuge, a disk centrifuge and a ceramic membrane in the step (6) are purchased through commercial paths, and the technological parameters are well known in the art and have no special requirements.
Preferably, the UHT sterilization temperature in step (7) is 100-115 ℃ and the sterilization time is 2-30 seconds. The aim of using UHT to sterilize ceramic membrane filtrate is to kill microorganisms possibly existing in the ceramic membrane filtrate (because materials are inevitably exposed in the air in the processes of horizontal screw centrifugation, disc centrifugation and ceramic membrane filtration, and the risk of bacteria contamination) so as to ensure that the subsequent chromatography step cannot grow microorganisms and cannot cause degradation of mogroside.
The macroporous adsorption resin in the step (8) refers to macroporous adsorption resin commonly used in industry during extraction of fructus momordicae, such as D101 type, AB-8 type and the like. The volume usage of the macroporous adsorption resin is 0.15-0.25 times of the mass of the fresh momordica grosvenori, and the unit is cubic meters: tons.
Preferably, in the step (9), the alkali liquor is sodium hydroxide and/or potassium hydroxide aqueous solution with the mass percent concentration of 0.3% -0.5%, and the dosage of the alkali liquor is 1-3BV. After the macroporous resin is adsorbed, the resin column is washed by dilute alkali liquor to remove the flavonoid compounds, pigments, pesticide residues and other impurities adsorbed in the macroporous resin column, thereby improving the content of the products in the subsequent steps and improving the color of the products. If the concentration of the alkali liquor is too low or the dosage is too small, the aim cannot be achieved; if the concentration of the alkali solution is too high or the dosage is too high, a small amount of mogroside may be eluted, so that the yield of the mogroside is low.
Preferably, in step (10) and step (11), the modified activated carbon is activated carbon subjected to an activation modification treatment comprising the steps of: uniformly mixing active carbon and an activating agent, grinding into powder, presintering at 300-400 ℃ for 1-2h under inert atmosphere, removing water in the material, activating at 600-700 ℃ for 3-5h, cooling to room temperature after activation, neutralizing with dilute acid (such as dilute hydrochloric acid), soaking in hot water under ultrasonic condition, and finally washing to be neutral (pH is 6-7); the modifier is KOH and potassium permanganate according to the mass ratio of 10-15: 1.
Further, the dosage of the activating agent is 0.5-0.8 times of the mass of the activated carbon, the powder is ground into particles with the size of 0.5-2mm, the size is not too small, otherwise, the strength of the modified activated carbon is lower, and the regeneration of the activated carbon is not facilitated; the size is not too large, otherwise, the modification is not thorough, and the pesticide residue adsorption effect after the modification is reduced.
Further, the hot water washing under the ultrasonic condition is to use 70-90 ℃ hot water for soaking for 1-2 hours under the ultrasonic power of 300-500W and the ultrasonic frequency of 120-180kHz, and the soaking time is changed for 1-3 times. The pore canal of the activated carbon is still occupied by non-bulk substances if the activated carbon is not subjected to washing treatment. The key to obtaining high specific surface area activated carbon is that, in addition to the choice of active agent, subsequent water washing removes non-bulk materials. The invention uses hot water for impregnation under the ultrasonic condition, can save water quantity and effectively and thoroughly remove non-bulk substances in the active carbon pore canal.
In the prior art, KOH is generally adopted for activating the activated carbon, and generated steam is utilized to diffuse in a carbon layer at a proper activation temperature to form a new pore structure and generate new micropores. However, the activation method consumes a large amount of KOH, and even requires that the alkali-carbon ratio is more than 3 (KOH is more than 3 times of the mass of the activated carbon) for preparing the activated carbon with high specific surface area, so that on one hand, the serious waste of KOH is caused, and the large amount of KOH can aggravate the corrosion to equipment, and a large amount of acid washing is required to be carried out to neutrality, so that the production cost is too high. The prior art adopts a novel activation mode such as carbon dioxide, water vapor and the like, but equipment is expensive, operation conditions are strict, activation time is long, most of laboratory small-scale theoretical researches exist at present, and the method is not suitable for industrial production. The invention creatively uses KOH and potassium permanganate as the activating agent, which obviously reduces the dosage of KOH and reduces the activating temperature; the inventor also does not expect to find that the modified activated carbon obtained after adding a certain amount of potassium permanganate has enhanced adsorption capacity to organic matters, and the possible reason is that after adding the potassium permanganate, the activated carbon has a certain oxygen-containing active functional group, thereby being beneficial to adsorbing the organic matters of pesticide residues.
The activated carbon is not particularly limited, and in one embodiment of the present invention, the activated carbon before modification has a specific surface area of 400 to 800m 2 And/g. Commercially available activated carbon generally has the above range, and micropores (< 2 nm) and mesopores (2-50 nm) on activated carbon play a major role in the adsorption of pesticide residues. The specific surface area of the activated carbon after the activation and modification treatment is obviously increased to 2000m 2 Above/g, it is demonstrated that during the modification process, there is a reactionMore micropores and mesopores are formed, so that pesticide residues can be adsorbed more effectively.
Preferably, in the step (10), the volume percentage concentration of the moderate ethanol aqueous solution is 30-45vol%, and the dosage of the moderate ethanol is 3-5BV. The aim of using the moderate ethanol for elution is to obtain an eluted product with relatively large quantity and relatively high content of mogroside V. If the concentration of the moderate ethanol is too low or the dosage is too low, the quantity of the mogroside V in the eluted product (namely the first Siraitia grosvenorii extract) is small and the content is low; if the concentration of the medium ethanol is too high or the dosage is too high, the components adsorbed by the macroporous resin can be completely eluted, so that no or little product is generated in the subsequent high ethanol elution step.
Preferably, in the step (10), the amount of the modified activated carbon is 0.05-0.1wt% of the weight of the fresh fructus momordicae, the heating temperature is 60-90 ℃, and the stirring time is 1-3 hours. If the amount of the modified activated carbon is too small, the heating temperature is too low or the stirring time is too short, the above-mentioned objects cannot be sufficiently achieved; if the modified activated carbon is excessively used, the heating temperature is excessively high or the stirring time is excessively long, not only the waste of materials and energy sources can be caused, but also the loss of the mogroside can be caused.
Preferably, in the step (11), the volume percentage concentration of the high-grade ethanol is 50-75vol%, and the dosage of the high-grade ethanol is 1-3BV. The purpose of using the high-grade ethanol for elution is to completely elute the components which are not eluted completely by the medium-grade ethanol, so as to obtain an eluted product with relatively small quantity and relatively low content of mogroside V. If the concentration of the high ethanol is too low or the dosage is too low, the mogroside is likely to be eluted incompletely, so that the overall yield of the mogroside is low; if the concentration of the high ethanol is too high or the dosage is too high, the solvent and the energy source are wasted.
Preferably, in the step (11), the amount of the modified activated carbon is 0.02-0.05wt% of the weight of the fresh fructus momordicae, the heating temperature is 60-90 ℃, and the stirring time is 1-3 hours.
In the invention, the slow-release oxidant is adopted in the early stage, so that the effect of removing the oxidizable pesticide residues is better, the dosage of the modified activated carbon used in the subsequent modified activated carbon adsorption stage can be further reduced, the production cost is reduced, and the method is more suitable for industrial preparation.
In the present application, 1 bv=1 resin column volume.
The principle of the method of the invention is as follows:
pesticide residues in the momordica grosvenori mainly originate from direct spraying residues and indirect air, soil and water pollution. Firstly, in the step of de-enzyming, the whole fresh momordica grosvenori is soaked in hot water of a slow-release oxidant for a long time, so that the aim of removing most pesticide residues on the surface of the momordica grosvenori can be fulfilled, and the sweet glycoside in the momordica grosvenori cannot be adversely affected; the superheated water pulping treatment can obviously reduce the water consumption, increase the yield of the mogroside and prevent microbial pollution and breeding; secondly, before the macroporous adsorption resin is eluted by ethanol, washing impurities by alkali liquor can continuously remove pesticide residues; and finally, adding the modified activated carbon into the ethanol desorption solution, heating and stirring, and playing the adsorption effect of the activated carbon on pesticide residues and impurities to the greatest extent (the adsorption effect of the activated carbon on pesticide residues in an alcohol phase is superior to that of a water phase). The invention thoroughly and thoroughly modifies the organophosphorus pesticide residues by using the slow-release oxidant, and then the adsorption capacity of the activated carbon on the pesticide residues is obviously improved, so that the pesticide residues in the Siraitia grosvenorii extract are thoroughly removed.
The method has the beneficial effects that:
(1) The slow-release oxidant is prepared, so that a large amount of pesticide residues which are easy to oxidize can be effectively removed in the enzyme deactivation stage of the momordica grosvenori, the consumption of the activated carbon in the subsequent activated carbon adsorption process is reduced, and the purposes of thoroughly removing the pesticide residues and improving the yield of the momordica grosvenori sweet glycoside are achieved.
(2) The invention can thoroughly remove pesticide residues through modifying the activated carbon, achieves the purpose of high-quality fructus momordicae extract, meets the market requirements of export international market high-end food additives, sweeteners and the like, and has high product overflow price.
(3) The invention carries out the pulping extraction of the momordica grosvenori by the superheated water, thereby increasing the yield of the momordica grosvenori sweet glycoside.
(4) The method can simultaneously obtain two pesticide residue-free momordica grosvenori extract products with different content specifications, and can meet the requirements on the content, quality, color, taste and the like of mogrosides; the method of the invention carries out process allocation on the content and the proportion of various sweet glycosides (mainly six sweet glycosides) in the momordica grosvenori, and the proportion and the content of various sweet glycosides in the finally obtained two-specification products are optimized, thereby meeting different consumption scenes and demands.
(5) The method perfectly integrates three technological means for removing pesticide residues in the whole production and processing process of the momordica grosvenori extract, and saves the production and processing cost on the premise of ensuring that the pesticide residue index of the product is qualified.
(6) The method adopts the key operation steps and combination of original complete fresh fruit fixation, overheated (alkali) water beating and midway UHT sterilization, so that the yield of the mogroside V is high, and the taste of the momordica grosvenori extract is not influenced.
Detailed Description
The invention is further illustrated below with reference to examples.
Fresh momordica grosvenori used in the embodiment of the invention is purchased from Guangxi Guilin, wherein the mass percentage content of 11-O-glycoside V of momordica grosvenori is 0.045wt%, the mass percentage content of mogroside V is 0.491wt%, the mass percentage content of mogroside VI is 0.028wt%, the mass percentage content of mogroside is 0.016wt%, the mass percentage content of mogroside IV is 0.013wt%, the mass percentage content of mogroside III is 0.006wt%, and the mass percentage content of total mogroside is 0.599wt%; the decanter centrifuge and the disk centrifuge used in the embodiment of the invention are purchased from Jiangsu Tong mechanical Co., ltd; the ceramic membrane used in the embodiment of the invention is purchased from Nanjing Fulin environmental protection technology Co., ltd; the macroporous adsorption resin used in the embodiment of the invention is purchased from Siam blue dawn technology new material Co., ltd; the raw materials or chemical reagents used in the examples of the present invention, unless otherwise specified, were obtained by conventional commercial means.
Unmodified activated carbon obtained from Jiangsu Su Qitan scientific and technological Co., ltd, is in the form of 3-5mm granule with specific surface area of about 800m 2 /g。，
In the embodiment of the invention, the content of mogroside V is detected by adopting a High Performance Liquid Chromatography (HPLC) external standard method; and detecting pesticide residues by adopting a liquid chromatography and gas chromatography-mass spectrometry (GC-MS).
Preparation example 1
10kg of granular commercially available activated carbon (bet=800 m 2 Uniformly mixing/g) and 5kg of modifier (mixture of KOH and potassium permanganate according to the mass ratio of 10:1), grinding into powder with the size of about 1mm, putting into an intelligent temperature-controlled heating furnace, pre-burning the heating furnace for 2 hours at 300 ℃ with water content less than 0.1%, heating to 600 ℃, preserving heat and activating for 5 hours, cooling to room temperature, neutralizing with 1wt% of dilute hydrochloric acid, putting into an ultrasonic cleaner, putting into 90 ℃ hot water, immersing for 2 hours under ultrasonic conditions (300W, 150 kHz), and replacing the hot water for 2 times; finally, washing until the pH value of the washing liquid is 6.8, taking out, and drying to obtain the modified activated carbon. The modified activated carbon obtained in preparation example 1 was tested according to GB/T7702.20-2008 for specific surface area (BET) of 2420m 2 /g。
Preparation example 2
10kg of granular commercially available activated carbon (bet=800 m 2 Uniformly mixing/g) and 8kg of modifier (mixture of KOH and potassium permanganate according to the mass ratio of 15:1), grinding into powder with the size of about 1mm, putting into an intelligent temperature-controlled heating furnace, pre-burning the heating furnace for 1h at 400 ℃ with the water content less than 0.1%, heating to 700 ℃, preserving heat and activating for 3h, cooling to room temperature, neutralizing with 1wt% of dilute hydrochloric acid, putting into an ultrasonic cleaner, putting into 90 ℃ of hot water, immersing for 2h under ultrasonic conditions (300W, 180 kHz), and replacing the hot water for 2 times; finally, washing until the pH value of the washing liquid is 6.7, taking out, and drying to obtain the modified activated carbon. The modified activated carbon obtained in preparation example 2 was tested according to GB/T7702.20-2008 for specific surface area (BET) of 2260m 2 /g。
Preparation example 3
(1) 1 molar part of calcium chloride is dissolved in ethanol water solution (the volume ratio of ethanol to water is 3:7) with the mass of 5 times, the solution is filtered, and chlorine is added into the filtratePEG1200 with 5wt% of calcium carbide and 25wt% of ammonia water are added, the pH of the system is 9.6, 30wt% of hydrogen peroxide is slowly added dropwise under the stirring condition of 200rpm, and the hydrogen peroxide consumption is 4.2 molar parts (in terms of H 2 O 2 Dropwise adding NaOH/KOH solution to enable the pH value of the system to be 12, generating white precipitate, carrying out suction filtration, washing with absolute ethyl alcohol for three times, and carrying out vacuum freeze-drying under the condition of 80 ℃ below zero and 100Pa to obtain nano calcium peroxide with the particle size D50 of 120nm;
(2) 20 parts by mass of polyvinyl alcohol (with the number average molecular weight of about 5 ten thousand) and 8 parts by mass of polyhydroxyalkanoate (with the number average molecular weight of about 6000) are dissolved in 100 parts by mass of ethanol water solution (the volume ratio of ethanol to water is 1:1), 10 parts by mass of the superfine calcium peroxide powder prepared in the step (1) are added in 3 batches under the ultrasonic condition of 60kHz, stirred for 1h under the condition of 800rpm, and freeze-dried for 10h under the temperature of-60 ℃ and the pressure of 100Pa, so that the slow-release oxidant is obtained.
Comparative preparation example 1
10kg of granular commercially available activated carbon (bet=800 m 2 Uniformly mixing/g) with 30kg KOH, grinding into powder with the size of about 1mm, putting into an intelligent temperature-controlled heating furnace, filling nitrogen into the heating furnace in advance, presintering at 400 ℃ for 1h, keeping the water content less than 0.1%, heating to 700 ℃, preserving heat and activating for 3h, cooling to room temperature, neutralizing with 1wt% dilute hydrochloric acid, putting into an ultrasonic cleaner, putting into 90 ℃ hot water, immersing for 2h under ultrasonic conditions (300W, 180 kHz), and replacing hot water for 2 times; finally, washing until the pH value of the washing liquid is 6.7, taking out, and drying to obtain the modified activated carbon. The modified activated carbon obtained in comparative preparation example 1 was tested according to GB/T7702.20-2008 for a specific surface area (BET) of 1700m 2 /g。
Example 1
(1) Fresh fruit de-enzyming: selecting 2 tons of mature and complete fresh fructus momordicae, putting the fresh fructus momordicae into hot water with the temperature of 60 ℃ and containing 2 weight percent of the slow-release oxidant prepared in the preparation example 3, fully immersing the fresh fructus momordicae in the hot water, soaking for 4 hours, and then fishing out the fresh fructus momordicae from the hot water to obtain the de-enzymed fresh fructus momordicae;
(2) Pulping and extracting: adding the de-enzymed fresh fruits into a beating machine at a feeding speed of 1 ton/hour, and simultaneously introducing superheated water at a temperature of 105 ℃ at a flow speed of 1 ton/hour, and beating and extracting to obtain beating extract; collecting the extracted slag for later use;
(3) Countercurrent extraction: countercurrent extraction is carried out on the pulped extraction slag, the water consumption is 3 tons, the extraction temperature is 94 ℃, and countercurrent extraction liquid is obtained;
(4) Horizontal screw centrifugation: mixing the beating extract and the countercurrent extract, and filtering with a horizontal decanter centrifuge (rotation speed of 5000 rpm) to obtain horizontal decanter centrifuge filtrate;
(5) Disc centrifugation: filtering the horizontal spiral centrifugal filtrate by a disc type centrifugal machine (6000 rpm) to obtain disc type centrifugal filtrate;
(6) And (3) ceramic membrane filtration: filtering the disc-type centrifugal filtrate with an alumina ceramic membrane (0.2 μm) to obtain ceramic membrane filtrate;
(7) And (3) sterilization: sterilizing the ceramic membrane filtrate with UHT equipment at 110deg.C for 10 seconds, and cooling to obtain sterilized material;
(8) Macroporous resin adsorption: passing the sterilized material through a D101 macroporous adsorption resin column, wherein the column volume is 1.0 cubic meter and 1BV;
(9) Removing impurities: after the macroporous resin is adsorbed on the column, washing the resin column with 2BV of NaOH aqueous solution with the mass percent concentration of 0.5wt%, and washing the resin column with pure water until the resin column is neutral;
(10) Gradient elution I: eluting macroporous adsorption resin column with 4BV of 35% ethanol, adding 1.7kg of modified activated carbon prepared in preparation example 1 into the eluate, heating to 70deg.C, stirring for 3 hr, filtering, concentrating, and drying to obtain 15.07kg of first fructus Siraitiae Grosvenorii extract;
(11) Gradient elution II: eluting with 72% ethanol by volume of 2BV, adding 0.8kg of the active carbon prepared in preparation example 1 into the ethanol eluate, heating to 70deg.C, stirring for 3 hr, filtering, concentrating, and drying to obtain 5.60kg of second Siraitia grosvenorii extract.
The content of the mogroside V in the first momordica grosvenori extract obtained in the example 1 is 5.28 wt%, the content of the mogroside V is 52.32wt%, the content of the mogroside VI is 2.98 wt%, the content of the mogroside is 1.50 wt%, the content of the mogroside IV is 0.85 wt%, the content of the mogroside III is 0.50 wt%, and the content of the total mogroside is 63.43wt%, which are detected by a high performance liquid HPLC external standard method; the second Siraitia grosvenorii extract obtained in this example had a content of Siraitia grosvenorii 11-O glycoside V of 0.71% by weight, a content of Siraitia grosvenorii glycoside V of 24.91% by weight, a content of Siraitia grosvenorii glycoside VI of 1.05% by weight, a content of Siraitia grosvenorii siamese glycoside of 1.23% by weight, a content of Siraitia grosvenorii glycoside IV of 1.96% by weight, a content of Siraitia grosvenorii glycoside III of 0.62% by weight, and a content of Siraitia grosvenorii total glycoside of 30.48% by weight. Through calculation, the total yield of the mogroside V is 94.50%, and the total yield of the mogroside is 94.04%.
The residue detection results of the first fructus momordicae extract and the second fructus momordicae extract obtained in the embodiment are: not detected. Wherein no organophosphorus (methamidophos, omethoate, dimethoate, phorate, diazinon, parathion, methyl parathion, malathion, aqueous amifos, quinofos, endo-phosphate, trichlorfon) was detected.
Example 2
(1) Fresh fruit de-enzyming: selecting 2 tons of mature and complete fresh fructus momordicae, putting the fresh fructus momordicae into 50 ℃ hot water containing 3wt% of the slow-release oxidant prepared in preparation example 4, fully immersing the fresh fructus momordicae in the hot water, soaking for 6 hours, and fishing out the fresh fructus momordicae from the hot water to obtain the de-enzymed fresh fructus momordicae;
(2) Pulping and extracting: adding the de-enzymed fresh fruits into a beating machine at a feeding speed of 1 ton/hour, and simultaneously introducing superheated water at 105 ℃ at a flow speed of 1.5 tons/hour, and beating and extracting to obtain beating extract; collecting the extracted slag for later use;
(3) Countercurrent extraction: countercurrent extraction is carried out on the pulped extraction slag, the water consumption is 4 tons, and the extraction temperature is 90 ℃ to obtain countercurrent extraction liquid;
(4) Horizontal screw centrifugation: mixing the beating extract and the countercurrent extract, and filtering with a horizontal decanter centrifuge to obtain horizontal decanter centrifuge filtrate;
(5) Disc centrifugation: filtering the horizontal spiral centrifugal filtrate by a disc type centrifugal machine to obtain disc type centrifugal filtrate;
(6) And (3) ceramic membrane filtration: filtering the disc-type centrifugal filtrate by using a ceramic membrane to obtain ceramic membrane filtrate;
(7) And (3) sterilization: sterilizing the ceramic membrane filtrate with UHT equipment at 105deg.C for 12 seconds, and cooling to obtain sterilized material;
(8) Macroporous resin adsorption: passing the sterilized material through a D101 macroporous adsorption resin column, wherein the column volume is 1.0 cubic meter and 1BV;
(9) Removing impurities: after the macroporous resin adsorption is finished, washing the resin column with a KOH aqueous solution with the mass percent concentration of 2BV of 0.5wt%, and washing the resin column with pure water until the resin column is neutral;
(10) Gradient elution I: eluting with 3.5BV of 38% ethanol by volume, adding 2kg of activated carbon prepared in preparation example 2 into the eluate, heating to 80deg.C, stirring for 2 hr, filtering, concentrating, and drying to obtain 15.93kg of first fructus Siraitiae Grosvenorii extract;
(11) Gradient elution II: eluting with 70% ethanol by volume of 1.5BV, adding 1.2kg of preparation example 2 to the eluate, heating to 80deg.C, stirring for 2 hr, filtering, concentrating, and drying to obtain 4.08kg of second fructus Siraitiae Grosvenorii extract.
The content of the momordica grosvenori 11-O-glycoside V of the first momordica grosvenori extract obtained in the embodiment is 5.04wt%, the content of the momordica grosvenori stevioside V is 50.36wt%, the content of the momordica grosvenori stevioside VI is 2.84wt%, the content of the momordica grosvenori siamenoside is 1.35wt%, the content of the momordica grosvenori stevioside IV is 0.82wt%, the content of the momordica grosvenori stevioside III is 0.45wt%, and the content of the total momordica grosvenori glycoside is 60.86wt% through the detection of a high performance liquid phase HPLC external standard method; the second Siraitia grosvenorii extract obtained in this example had a content of Siraitia grosvenorii 11-O-glycoside V of 0.65wt%, a content of Siraitia grosvenorii glycoside V of 26.75%, a content of Siraitia grosvenorii glycoside VI of 1.54wt%, a content of Siraitia grosvenorii siamese glycoside of 1.86wt%, a content of Siraitia grosvenorii glycoside IV of 2.67wt%, a content of Siraitia grosvenorii glycoside III of 0.97wt% and a content of Siraitia grosvenorii total glycoside of 34.44wt%. Wherein, the total yield of the mogroside V is 92.80 percent and the total yield of the mogroside V is 92.65 percent.
The residue detection results of the first fructus momordicae extract and the second fructus momordicae extract obtained in the embodiment are: not detected. Wherein no organophosphorus (methamidophos, omethoate, dimethoate, phorate, diazinon, parathion, methyl parathion, malathion, aqueous amifos, quinofos, endo-phosphate, trichlorfon) was detected.
Comparative example 1
Step (10) and step (11) the activated carbon prepared in comparative preparation example 1 was used, and the operation of the remaining steps was the same as in example 1.
Detecting 400 items of pesticide residues by liquid chromatography and gas chromatography-mass spectrometry (GC-MS), wherein the pesticide residue detection result of the first Siraitia grosvenorii extract obtained by the method is as follows: dimethomorph 0.23mg/kg, iprodione 0.11mg/kg, oxadixyl 0.05mg/kg, propamocarb and propamocarb salts 0.27mg/kg, other items below the limit of quantification or undetected;
the pesticide residue detection result of the second fructus momordicae extract in this example is: dimethomorph 0.12mg/kg, iprodione 0.06mg/kg, oxadixyl 0.05mg/kg, propamocarb and propamocarb salts 0.22mg/kg, other items below the quantitative limit or undetected
Comparative example 2
The pulping and extracting in the step (2) is changed into: adding the de-enzymed fresh fruits into a beating machine at a feeding speed of 1 ton/hour, and simultaneously introducing hot water at 70 ℃ at a flow speed of 3 tons/hour, and beating and extracting to obtain beating extract; collecting the extracted slag for later use; the operation of the remaining steps was identical to example 1. Namely, the superheated water beating extraction in the step (2) is changed into warm water beating extraction.
14.41kg of the first momordica grosvenori extract and 5.27kg of the second momordica grosvenori extract are finally obtained.
The content of mogroside V in the first Siraitia grosvenorii extract obtained in the example is 49.06 percent and the content of total mogroside is 60.18 percent through high performance liquid HPLC external standard detection; the obtained second fructus Siraitiae Grosvenorii extract has mogroside V content of 23.60% and fructus Siraitiae Grosvenorii total glycoside content of 29.25%; through calculation, the total yield of the mogroside V is 84.66%, and the total yield of the mogroside is 85.25%.
Comparative example 3
Other operations and conditions were the same as in example 1, except that in step (1), the slow-release oxidizing agent was charged instead of the same mass of calcium peroxide.
The final mogroside yield and purity were substantially unaffected and comparable to example 1. And detecting the residual agricultural items of the 400 items of the final product by a liquid chromatography and gas chromatography-mass spectrometry (GC-MS), wherein the content of methamidophos in the first fructus momordicae extract is 0.11mg/kg, and the content of methamidophos in the second fructus momordicae extract is 0.07mg/kg.
Comparative example 4
The "gradient elution I" step in step (10) was not performed, and the operations of the remaining steps were identical to those of example 1 (i.e., gradient elution was not performed, elution was directly performed with high ethanol), and the only Siraitia grosvenorii extract 20.11kg was finally obtained.
The content of the momordica grosvenori 11-O-glycoside V of the unique momordica grosvenori extract obtained in the example is 4.13wt%, the content of the momordica grosvenori stevioside V is 44.68wt%, the content of the momordica grosvenori stevioside VI is 2.57wt%, the content of the momordica grosvenori siamenoside is 1.45wt%, the content of the momordica grosvenori stevioside IV is 1.17wt%, the content of the momordica grosvenori stevioside III is 0.54wt% and the total content of the stevioside is 54.54wt% through the detection of a high performance liquid phase HPLC external standard method. Wherein, the yield of mogroside V is 91.50 percent and the yield of mogroside is 91.55 percent.
Claims (10)
1. An improved co-production method of a pesticide residue-free momordica grosvenori sweet glycoside composition is characterized by comprising the following steps of:
(1) Fresh fruit de-enzyming: soaking the whole fresh fructus Siraitiae Grosvenorii in hot water containing slow release oxidant, completely immersing, and taking out to obtain de-enzymed fresh fructus Siraitiae Grosvenorii; the slow-release oxidant is obtained by compounding polyvinyl alcohol and polyhydroxy fatty acid encapsulated superfine calcium peroxide;
(2) Pulping and extracting: adding the de-enzymed fresh fruits into a beating machine, and simultaneously, introducing hot water, and beating and extracting to obtain beating extract; collecting the extracted slag for later use;
(3) Countercurrent extraction: countercurrent extraction is carried out on the pulped extraction residues to obtain countercurrent extraction liquid;
(4) Horizontal screw centrifugation: mixing the beating extract and the countercurrent extract, and filtering with a horizontal decanter centrifuge to obtain horizontal decanter centrifuge filtrate;
(5) Disc centrifugation: filtering the horizontal spiral centrifugal filtrate by a disc type centrifugal machine to obtain disc type centrifugal filtrate;
(6) And (3) ceramic membrane filtration: filtering the disc-type centrifugal filtrate by using a ceramic membrane to obtain ceramic membrane filtrate;
(7) And (3) sterilization: sterilizing the ceramic membrane filtrate by UHT equipment, and cooling to obtain sterilized materials;
(8) Macroporous resin adsorption: passing the sterilized material through a macroporous adsorption resin column;
(9) Removing impurities: after the macroporous resin adsorption is finished, washing the resin column with dilute alkali liquor, and washing the resin column with pure water until the resin column is neutral;
(10) Gradient elution I: eluting with a macroporous adsorbent resin column with a moderate ethanol aqueous solution, adding modified activated carbon into the moderate ethanol eluent, heating, stirring, filtering, concentrating and drying to obtain a first fructus Siraitiae Grosvenorii extract;
(11) Gradient elution II: eluting with high ethanol water solution, adding modified activated carbon into the high ethanol eluate, heating, stirring, filtering, concentrating, and drying to obtain second fructus Siraitiae Grosvenorii extract;
the modified activated carbon is obtained by water washing activated carbon after activated carbon is activated at high temperature by an activating agent, wherein the activating agent comprises KOH and potassium permanganate.
2. The co-production method according to claim 1, wherein the slow-release oxidant is obtained by a preparation method comprising the steps of: dissolving polyvinyl alcohol and polyhydroxy fatty acid in an alcohol water solution, adding superfine calcium peroxide under the condition of ultrasonic stirring, uniformly dispersing, and freeze-drying a dispersion liquid to prepare a slow-release oxidant;
further, the mass ratio of the polyvinyl alcohol to the polyhydroxy fatty acid to the alcohol aqueous solution to the superfine calcium peroxide is 20-30:5-8:100-160:10-15.
3. The co-production method according to claim 2, wherein the particle size of the ultrafine calcium peroxide is 50-200nm; the preparation method of the superfine calcium peroxide comprises the following steps: dissolving calcium chloride in an alcohol water solution, filtering, adding a surfactant and ammonia water into the filtrate, slowly dropwise adding hydrogen peroxide under the stirring condition, dropwise adding NaOH/KOH solution to generate white precipitate, filtering, washing, and performing vacuum freeze drying to obtain nano calcium peroxide;
further, the molar ratio of the calcium chloride to the hydrogen peroxide is 3-5:1, and the mass concentration of the hydrogen peroxide is 20-35wt%; the surfactant is selected from PEG with number average molecular weight of 1000-2000, and the addition amount of the surfactant is 3-6wt% of the mass of calcium chloride; the mass concentration of the ammonia water is 20-30%, and the pH value of the system is adjusted to 9-10 by adding the ammonia water; slowly dropwise adding hydrogen peroxide within 1-2h; the mass concentration of NaOH/KOH solution is 1-5wt%, and the addition amount makes the pH of the system 11-12; the alcohol water solution is obtained by mixing ethanol and deionized water, wherein the volume content of the ethanol is 30-50%;
further, the ultrasonic stirring condition is stirring at 30-60kHz and 600-1000 rpm; the freeze drying is that the dispersion is freeze dried for 5-10 hours at the temperature of-60 ℃ to-30 ℃ and the pressure of 10-100 Pa.
4. The co-production method according to claim 1, wherein in the step (1), the temperature of the hot water is 50-60 ℃ and the soaking time is 3-6 hours; the mass concentration of the slow-release oxidant is 2-3wt%.
5. The co-production process according to claim 1, wherein in step (2) the superheated water has a temperature of 102-115 ℃, preferably 105-110 ℃; the dosage of the superheated water is 1-1.5 times of the weight of the fresh fructus momordicae.
6. The co-production method according to claim 1, wherein in the step (3), the water content of the countercurrent extraction is 1.5-3 times of the weight of fresh fruits of momordica grosvenori, and the extraction temperature is 85-95 ℃;
the UHT sterilization temperature in the step (7) is 100-115 ℃, and the sterilization time is 2-30 seconds;
the macroporous adsorption resin in the step (8) is D101 type or AB-8 type, the volume dosage of the macroporous adsorption resin is 0.15-0.25 times of the mass of the fresh fructus momordicae, and the unit is cubic meters: ton of water;
in the step (9), the alkali liquor is sodium hydroxide and/or potassium hydroxide aqueous solution with the mass percent concentration of 0.3-0.5%, and the dosage of the alkali liquor is 1-3BV.
7. The co-production method according to claim 1, wherein in step (10) and step (11), the modified activated carbon is activated carbon subjected to an activation modification treatment comprising the steps of: uniformly mixing active carbon and an activating agent, grinding into powder, presintering for 1-2 hours at 300-400 ℃ under inert atmosphere, removing water in the material, activating for 3-5 hours at 600-700 ℃, cooling to room temperature after activation, neutralizing with dilute acid, soaking with hot water under ultrasonic condition, and finally washing with water to be neutral; the modifier is KOH and potassium permanganate according to the mass ratio of 10-15: 1.
8. The co-production method according to claim 7, wherein the amount of the activator is 0.5 to 0.8 times the mass of the activated carbon, and the grinding into powder is grinding into particles having a size of 0.5 to 2 mm.
9. The co-production method according to claim 7, wherein the hot water washing under the ultrasonic condition is performed by soaking with hot water at 70-90 ℃ for 1-2 hours under the ultrasonic power of 300-500W and the ultrasonic frequency of 120-180 kHz;
further, the specific surface area of the activated carbon before modification is 400-800m 2 /g; the specific surface area of the modified active carbon is 2000m 2 And/g.
10. The co-production method according to claim 1, wherein in the step (10), the volume percentage concentration of the aqueous medium ethanol solution is 30-45vol%, and the amount of the medium ethanol is 3-5BV; preferably, in the step (10), the amount of the modified activated carbon is 0.05-0.1wt% of the weight of the fresh fructus momordicae, the heating temperature is 60-90 ℃, and the stirring time is 1-3 hours;
in the step (11), the volume percentage concentration of the high-grade ethanol is 50-75vol%, and the dosage of the high-grade ethanol is 1-3BV; preferably, in the step (11), the amount of the modified activated carbon is 0.02-0.05wt% of the weight of the fresh fructus momordicae, the heating temperature is 60-90 ℃, and the stirring time is 1-3 hours.
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