CN116941765B - An improved method for co-producing a pesticide-free mogroside composition - Google Patents
An improved method for co-producing a pesticide-free mogroside composition Download PDFInfo
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Abstract
本发明涉及一种改进的无农残罗汉果甜苷组合物的联产方法，是罗汉果浸泡在含有缓释氧化剂的热水中完成杀青，之后进行打浆提取、逆流提取、卧螺离心、碟式离心、陶瓷膜过滤、灭菌、大孔树脂吸附、稀碱液和水依次冲洗树脂柱除杂、中度乙醇进行梯度洗脱I、高度乙醇水溶液进行梯度洗脱II、洗脱液入改性活性炭。按照本发明方法制备得到的提取物，无农残，罗汉果苷收率高，是一种高品质的罗汉果提取物。本发明工艺设备要求简单，可连续化操作，是一种适合工业化的罗汉果提取物的制备方法。The present invention relates to an improved method for co-producing a mogroside composition without pesticide residues, wherein the mogroside is soaked in hot water containing a slow-release oxidant to complete the killing, followed by pulping extraction, countercurrent extraction, horizontal spiral centrifugation, disc centrifugation, ceramic membrane filtration, sterilization, macroporous resin adsorption, resin column washing with dilute alkali solution and water in sequence to remove impurities, gradient elution I with moderate ethanol, gradient elution II with high ethanol aqueous solution, and the eluent is added to modified activated carbon. The extract prepared according to the method of the present invention has no pesticide residues and a high yield of mogroside, and is a high-quality mogroside extract. The process equipment requirements of the present invention are simple, and continuous operation can be performed, and the method is a preparation method of the mogroside extract 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 the excessive use of activated carbon can cause loss of mogroside, the yield of the mogroside is low, the yield of the momordica grosvenori with unit mass is low, and the method has no cost advantage, and in addition, the method only has the effect of partially removing pesticide residues of carbendazim, and has no description on whether the pesticide residues of other types are effective.
CN201680034301.3 discloses a pesticide-free momordica grosvenori extract and a preparation method thereof, which takes the momordica grosvenori extract as a raw material, and obtains the pesticide-free momordica grosvenori extract 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 in a momordica grosvenori extract, which takes the momordica grosvenori extract as a raw material, and obtains the momordica grosvenori extract for removing pesticide residues, heavy metals and plasticizers through the steps of dissolution, 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 large-scale production method of mogroside for removing pesticide residue, which uses dried fructus momordicae as raw material, and obtains the mogroside for removing pesticide residue through 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. 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 simultaneously extracting mogroside without pesticide residue and water-soluble dietary fiber, which is characterized in that the momordica grosvenori is cleaned, boiled, chromatographed, ultrafiltered, nanofiltration and concentrated to obtain the mogroside 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 residue, which adopts hydrogen peroxide and alkali to deactivate green of the fresh Siraitia grosvenorii under the condition of hot water, and utilizes the oxidation of the hydrogen peroxide and the alkaline condition to facilitate the removal of pesticide residue on the surface of the Siraitia grosvenorii. 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, namely immersing complete fresh momordica grosvenori in hot water containing a slow-release oxidant, fully immersing, and fishing out to obtain de-enzymed fresh fruit, wherein the slow-release oxidant is obtained by compounding polyvinyl alcohol and polyhydroxy fatty acid encapsulated superfine calcium peroxide;
(2) Pulping and extracting, namely adding the de-enzymed fresh fruits into a pulping machine, and simultaneously introducing hot water, pulping and extracting to obtain a pulping extracting solution;
(3) Countercurrent extraction, namely countercurrent extracting the pulped extraction slag to obtain countercurrent extraction liquid;
(4) Horizontal screw centrifugation, namely mixing beating extracting solution and countercurrent extracting solution, and filtering by using a horizontal screw centrifuge to obtain horizontal screw centrifugal filtrate;
(5) Disc centrifugation, namely filtering the horizontal spiral centrifugal filtrate by using a disc centrifuge to obtain disc centrifugal filtrate;
(6) Ceramic membrane filtration, namely filtering the disc-type centrifugal filtrate by using a ceramic membrane to obtain ceramic membrane filtrate;
(7) Sterilizing the ceramic membrane filtrate with UHT equipment, and cooling to obtain sterilized material;
(8) Macroporous resin adsorption, namely passing the sterilized material through a macroporous adsorption resin column;
(9) Removing impurities, namely after macroporous resin adsorption is finished, washing a resin column by dilute alkali liquor, and washing the resin column to be neutral by pure water;
(10) Gradient eluting with aqueous medium ethanol, subjecting to macroporous adsorbent resin column eluting, adding modified activated carbon into the medium ethanol eluate, heating, stirring, filtering, concentrating, and drying to obtain first fructus Siraitiae Grosvenorii extract;
(11) Gradient eluting II, namely eluting the macroporous adsorption resin column by using a high-ethanol aqueous solution, adding modified activated carbon into the high-ethanol eluent, heating, stirring, filtering, concentrating and drying to obtain a second fructus momordicae 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 oxidant is prepared by the preparation method comprising the steps of dissolving polyvinyl alcohol and polyhydroxylated fatty acid in an alcohol water solution, adding superfine calcium peroxide under the condition of ultrasonic stirring, uniformly dispersing, and freeze-drying the dispersion liquid to prepare 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, the volume concentration of the alcohol in the alcohol aqueous 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.
The preparation method of the superfine calcium peroxide comprises the steps of dissolving calcium chloride in an alcohol water solution, filtering, adding a surfactant and ammonia water into 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.
The method comprises the steps of further adding calcium chloride and hydrogen peroxide in a molar ratio of 3-5:1, wherein the mass concentration of the hydrogen peroxide is 20-35wt%, the surfactant is PEG with the number average molecular weight of 1000-2000, the addition amount of the surfactant is 3-6wt% of the mass of the calcium chloride, the mass concentration of ammonia water is 20-30%, the addition amount of the ammonia water is used for adjusting the pH value of a system to 9-10, slowly adding hydrogen peroxide dropwise within 1-2h, the mass concentration of NaOH/KOH solution is 1-5wt% and the addition amount is used for enabling the pH value of the system to be 11-12, and the alcohol-water solution is obtained by mixing ethanol and deionized water, wherein the volume content of 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 600-1000rpm, and the freeze drying is that the dispersion is freeze dried at-60 ℃ to-30 ℃ and 10-100Pa for 5-10 hours.
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, the immersing time is 3-6 hours, and the mass concentration of the slow-release oxidant is 2-3wt%. Compared with the prior patent 202310284713.4 of the inventor, the process adopts the slow-release oxidant, reduces the temperature of hot water and prolongs the soaking time. 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 oxidative components in hot water and generates Ca (OH) 2, so that the system is slightly alkaline, and the removal of pesticide residues on the surface of the momordica grosvenori is facilitated. No inorganic base is added. The method has the advantages that the method is simple in structure, convenient to use, and easy to operate, and has the advantages of being convenient to use, and the fresh fruits of the momordica grosvenori are deactivated, various biological enzymes and proteins of the momordica grosvenori are deactivated, browning caused by Maillard reaction is prevented, so that the color of an extracting solution, a filtrate and a concentrated solution in each subsequent step is light, microorganisms such as endophytic fungi carried by the fresh fruits of the momordica grosvenori are killed, enzymes produced by the microorganisms possibly have negative effects on degradation of mogroside, and the alkaline aqueous solution can leach flavonoid compounds, phenolic acids, grease and most of pigment and pesticide residues in shells of the fresh fruits of the momordica grosvenori, so that most of impurities and pesticide residues are removed, the quality of materials in the subsequent steps is indirectly improved, the difficulty of separation and purification is reduced, and the quality and taste of products are improved.
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 pulping 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 finds that the advantage of pulping by using superheated water in the siraitia grosvenorii extraction process is that firstly, the water quantity is saved and most of the mogroside is leached, secondly, the extraction process is largely and rapidly completed, the production efficiency is improved, and thirdly, the pollution of external microorganisms is prevented and the degradation of the 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 macroporous adsorption resin is 0.15-0.25 times of the mass of fresh fructus Siraitiae Grosvenorii, and the unit is cubic meter per ton.
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, and if the concentration of the alkali liquor is too high or the dosage is too large, a small amount of mogroside can be eluted, so that the yield of the mogroside is low.
Preferably, in the step (10) and the step (11), the modified activated carbon is activated and modified by the steps of uniformly mixing the activated 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 by dilute acid (such as dilute hydrochloric acid), soaking by hot water under ultrasonic condition, and finally washing to neutrality (pH is 6-7), wherein the modifying agent is a mixture of KOH and potassium permanganate according to a mass ratio of 10-15:1.
Further, the usage amount of the activating agent is 0.5-0.8 times of the mass of the activated carbon, the powder is particles with the size of 0.5-2mm, the size is not required to be too small, otherwise, the strength of the modified activated carbon is low, the regeneration of the activated carbon is not facilitated, the size is not required to be too large, otherwise, the modification is not thorough, and the pesticide residue adsorbing 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 hot water is replaced for 1-3 times during the soaking period. 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 takes KOH and potassium permanganate as an activating agent, remarkably reduces the dosage of KOH and reduces the activation temperature, and 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, probably because the activated carbon after adding potassium permanganate has a certain oxygen-containing active functional group, thereby being beneficial to adsorbing pesticide residue organic matters.
The activated carbon is not particularly limited, and in one embodiment of the present invention, the specific surface area of the activated carbon before modification is 400 to 800m 2/g. Commercially available activated carbon generally plays a major role in the adsorption of pesticide residues in the micropores (< 2 nm) and mesopores (2-50 nm) on the activated carbon within the above-mentioned range. The specific surface area of the activated carbon subjected to the activation modification treatment is obviously increased to more than 2000m 2/g, and the activated carbon proves that more micropores and mesopores are formed in the modification process, 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 mogroside V in the eluted product (namely the first Siraitia grosvenorii extract) is small and the content of mogroside V in the eluted product is low, and if the concentration of the moderate ethanol is too high or the dosage is too high, the components adsorbed by the macroporous resin can be completely eluted, so that no product or very few products are 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 aim cannot be fully achieved, and if the amount of the modified activated carbon is too large, the heating temperature is too high or the stirring time is too long, not only the waste of materials and energy sources can be caused, but also the loss of the mogroside can be possibly 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 alcohol is too low or the dosage is too low, the mogroside can be incompletely eluted, so that the overall yield of the mogroside is low, and if the concentration of the high alcohol is too high or the dosage is too high, the waste of solvents and energy sources can be caused.
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 enzyme deactivation, 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, the sweet glycoside in the momordica grosvenori cannot be adversely affected, the use amount of water can be obviously reduced by beating treatment of the overheated water, the yield of the momordica grosvenori sweet glycoside can be increased, microbial pollution and breeding can be prevented, secondly, before macroporous adsorption resin is eluted by ethanol, the pesticide residues can be continuously removed by washing impurities by alkali liquor, and finally, modified activated carbon is added into ethanol desorption liquid and heated and stirred, so that the adsorption effect of the activated carbon on the pesticide residues and impurities (the adsorption effect of the activated carbon on the pesticide residues in an alcohol phase is superior to that of the water phase) can be furthest exerted. 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, can meet the requirements on the content, quality, color, taste and the like of the mogrosides, and can be used for carrying out process allocation on the content and the proportion of various steviosides (mainly six steviosides) in the momordica grosvenori, optimizing the proportion and the content of various steviosides in the finally obtained products with the two specifications, and meeting different consumption scenes and requirements.
(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 percent content of momordica grosvenori 11-O-glycoside V is 0.045wt%, the mass percent content of momordica grosvenori sweet glycoside V is 0.491wt%, the mass percent content of momordica grosvenori sweet glycoside VI is 0.028wt%, the mass percent content of momordica grosvenori siamenoside is 0.016wt%, the mass percent content of momordica grosvenori sweet glycoside IV is 0.013wt%, the mass percent content of momordica grosvenori sweet glycoside III is 0.006wt%, and the mass percent content of momordica grosvenori total glycoside is 0.599wt%, the horizontal decanter centrifuge and the disk centrifuge used in the embodiment of the invention are both purchased from Jiangsu-bang mechanical Co, the ceramic membrane used in the embodiment of the invention is purchased from Nanford environmental protection technology Co, the macroporous adsorption resin used in the embodiment of the invention is purchased from Siraitia grosvenori blue technology Co, and the raw materials used in the embodiment of the invention are purchased from Siraitia grosvenori blue technology Co, or the raw materials used in the embodiment are obtained by the invention through a special commercial method.
The unmodified activated carbon is purchased from Jiangsu Su Qitan, a scientific and technological company, and is in the form of 3-5mm granules, and the specific surface area is about 800m 2/g. ,
The embodiment of the invention adopts a high performance liquid chromatography HPLC external standard method to detect the content of mogroside V, and adopts a liquid chromatography and gas chromatography-mass spectrometry (GC-MS) to detect pesticide residues.
Preparation example 1
Mixing 10kg of commercial active carbon (BET=800 m 2/g) and 5kg of modifier (mixture of KOH and potassium permanganate according to mass ratio of 10:1), grinding into powder with the size of about 1mm, putting into an intelligent temperature-controlled heating furnace, filling nitrogen in advance, presintering at 300 ℃ for 2 hours and the water content of <0.1%, heating to 600 ℃, preserving heat and activating for 5 hours, cooling to room temperature, neutralizing with 1wt% of diluted hydrochloric acid, putting into an ultrasonic cleaning instrument, immersing for 2 hours under ultrasonic conditions (300W, 150 kHz) with 90 ℃ of hot water, replacing the hot water for 2 times, finally washing with water until the pH of the water washing liquid is 6.8, taking out, and drying to obtain the modified active 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
Mixing 10kg of commercial active carbon (BET=800 m 2/g) and 8kg of modifier (mixture of KOH and potassium permanganate according to mass ratio of 15:1) uniformly, grinding into powder with the size of about 1mm, putting into an intelligent temperature-controlled heating furnace, filling nitrogen in advance, presintering at 400 ℃ for 1h, keeping the water content below 0.1%, heating to 700 ℃, preserving heat and activating for 3h, cooling to room temperature, neutralizing with 1wt% of diluted hydrochloric acid, putting into an ultrasonic cleaning instrument, immersing in 90 ℃ hot water for 2h under ultrasonic conditions (300W, 180 kHz), replacing the hot water for 2 times, finally washing with water until the pH of the water washing liquid is 6.7, taking out, and drying to obtain the modified active 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) Dissolving 1 mol part of calcium chloride in 5 times of ethanol water solution (the volume ratio of ethanol to water is 3:7), filtering, adding PEG1200 accounting for 5wt% of calcium chloride and 25wt% of ammonia water into filtrate, slowly dropwise adding 30wt% of hydrogen peroxide under the stirring condition of 200rpm, dropwise adding 4.2 mol parts of hydrogen peroxide (calculated by H 2O2), dropwise adding NaOH/KOH solution to ensure that the pH of the system is 12, generating white precipitate, filtering, washing three times by absolute ethyl alcohol, freezing and drying under the vacuum condition of-80 ℃ 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 agent is obtained.
Comparative preparation example 1
Mixing 10kg of commercial active carbon (BET=800 m 2/g) with 30kg of KOH uniformly, grinding into powder with the size of about 1mm, putting into an intelligent temperature-controlled heating furnace, pre-burning the powder for 1h at 400 ℃ with water content of 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 cleaning instrument, putting into 90 ℃ of hot water, immersing for 2h under ultrasonic conditions (300W, 180 kHz), replacing the hot water for 2 times, finally washing until the pH of water washing liquid is 6.7, taking out, and drying to obtain the modified active 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, namely selecting 2 tons of mature and complete fresh fructus momordicae, putting the fresh fruit into 60 ℃ hot water containing 2wt% of the slow-release oxidant prepared in preparation example 3, fully immersing the fresh fruit in the hot water, soaking for 4 hours, and fishing out the fresh fruit from the hot water to obtain de-enzymed fresh fruit;
(2) Pulping and extracting, namely adding the de-enzymed fresh fruits into a pulping 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, pulping and extracting to obtain a pulping extracting solution;
(3) Countercurrent extraction, namely countercurrent extracting the pulped extraction slag with water consumption of 3 tons and extraction temperature of 94 ℃ to obtain countercurrent extraction liquid;
(4) Horizontal screw centrifugation, namely mixing beating extracting solution and countercurrent extracting solution, and filtering by using a horizontal screw centrifuge (rotating speed is 5000 rpm) to obtain horizontal screw centrifugal filtrate;
(5) Disc centrifugation, namely filtering the horizontal spiral centrifugal filtrate by using a disc centrifuge (6000 rpm) to obtain disc centrifugal filtrate;
(6) Ceramic membrane filtration, namely filtering disc-type centrifugal filtrate by an alumina ceramic membrane (0.2 μm) to obtain ceramic membrane filtrate;
(7) Sterilizing the ceramic membrane filtrate with UHT equipment at 110deg.C for 10 seconds, and cooling to obtain sterilized material;
(8) Macroporous resin adsorption, namely passing the sterilized material through a D101 macroporous adsorption resin column, wherein the column loading volume is 1.0 cubic meter and 1BV;
(9) Removing impurities, namely after the macroporous resin is adsorbed on the column, firstly flushing the resin column by using 2BV of NaOH aqueous solution with the mass percent concentration of 0.5wt%, and then flushing the resin column to be neutral by using pure water;
(10) Gradient elution I, namely eluting a macroporous adsorption resin column by using 4BV of moderate ethanol with the volume percentage concentration of 35%, adding 1.7kg of modified activated carbon prepared in preparation example 1 into the moderate ethanol eluent, heating to 70 ℃, stirring for 3 hours, filtering, concentrating and drying to obtain 15.07kg of first momordica grosvenori extract;
(11) Gradient elution II, namely eluting the macroporous adsorption resin column by using 2BV of high-concentration ethanol with the volume percentage concentration of 72%, adding 0.8kg of the active carbon prepared in the preparation example 1 into the high-concentration ethanol eluent, heating to 70 ℃, stirring for 3 hours, filtering, concentrating and drying to obtain 5.60kg of the second momordica grosvenori extract.
The content of mogroside V in the first Siraitia grosvenorii extract obtained in example 1 was 5.28 wt%, the content of mogroside V was 52.32wt%, the content of mogroside VI was 2.98 wt%, the content of mogroside IV was 1.50 wt%, the content of mogroside IV was 0.85 wt%, the content of mogroside III was 0.50 wt%, the content of mogroside total glycosides was 63.43wt%, the content of mogroside 11-O glycoside V in the second Siraitia grosvenorii extract obtained in this example was 0.71 wt%, the content of mogroside V was 24.91wt%, the content of mogroside VI was 1.05 wt%, the content of mogroside was 1.23 wt%, the content of mogroside IV was 1.96 wt%, the content of mogroside III was 0.62 wt%, and the content of mogroside total was 30.48wt%, as determined by high performance liquid HPLC external standard. Through calculation, the total yield of the mogroside V is 94.50%, and the total yield of the mogroside is 94.04%.
The detection of the residue of the pesticide error term mesh of the 400-item grosvenor momordica fruit by liquid chromatography and gas chromatography-mass spectrometry (GC-MS) shows that the pesticide residue detection results of the first and second grosvenor momordica fruit extracts 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, namely selecting 2 tons of mature and complete fresh fructus momordicae, putting the fresh fruit into 50 ℃ hot water containing 3wt% of the slow-release oxidant prepared in preparation example 4, fully immersing the fresh fruit in the hot water, soaking for 6 hours, and fishing out the fresh fruit from the hot water to obtain de-enzymed fresh fruit;
(2) Pulping and extracting, namely adding the de-enzymed fresh fruits into a pulping machine at a feeding speed of 1 ton/hour, and simultaneously introducing superheated water at a temperature of 105 ℃ at a flow speed of 1.5 tons/hour, pulping and extracting to obtain a pulping extract;
(3) Countercurrent extraction, namely countercurrent extracting the pulped extraction slag with water consumption of 4 tons and extraction temperature of 90 ℃ to obtain countercurrent extraction liquid;
(4) Horizontal screw centrifugation, namely mixing beating extracting solution and countercurrent extracting solution, and filtering by using a horizontal screw centrifuge to obtain horizontal screw centrifugal filtrate;
(5) Disc centrifugation, namely filtering the horizontal spiral centrifugal filtrate by using a disc centrifuge to obtain disc centrifugal filtrate;
(6) Ceramic membrane filtration, namely filtering the disc-type centrifugal filtrate by using a ceramic membrane to obtain ceramic membrane filtrate;
(7) Sterilizing the ceramic membrane filtrate with UHT equipment at 105 deg.C for 12 seconds, and cooling to obtain sterilized material;
(8) Macroporous resin adsorption, namely passing the sterilized material through a D101 macroporous adsorption resin column, wherein the column loading volume is 1.0 cubic meter and 1BV;
(9) Removing impurities, namely after macroporous resin adsorption is finished, washing a resin column by using a KOH aqueous solution with the mass percent concentration of 2BV of 0.5wt%, and washing the resin column to be neutral by using pure water;
(10) Gradient elution I, namely eluting a macroporous adsorption resin column by using 3.5BV of medium ethanol with the volume percentage concentration of 38%, adding 2kg of active carbon prepared in preparation example 2 into the medium ethanol eluent, heating to 80 ℃, stirring for 2 hours, filtering, concentrating and drying to obtain 15.93kg of first momordica grosvenori extract;
(11) And (2) gradient eluting II, namely eluting the macroporous adsorption resin column by using 70 percent ethanol with the volume percentage concentration of 1.5BV, adding 1.2kg of the preparation example 2 into the high ethanol eluent to prepare the active carbon, heating to 80 ℃, stirring for 2 hours, filtering, concentrating and drying to obtain 4.08kg of the second momordica grosvenori extract.
The content of the mogroside 11-O-glycoside V of the first Siraitia grosvenorii extract obtained in this example was 5.04wt%, the content of mogroside V was 50.36wt%, the content of mogroside VI was 2.84wt%, the content of mogroside was 1.35wt%, the content of mogroside IV was 0.82wt%, the content of mogroside III was 0.45wt%, the content of mogroside total glycosides was 60.86wt%, the content of mogroside 11-O-glycoside V of the second Siraitia grosvenorii extract obtained in this example was 0.65wt%, the content of mogroside V was 26.75%, the content of mogroside VI was 1.54wt%, the content of mogroside was 1.86wt%, the content of mogroside IV was 2.67wt%, the content of mogroside III was 0.97wt%, and the content of mogroside total glycosides was 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 detection of the residue of the pesticide error term mesh of the 400-item grosvenor momordica fruit by liquid chromatography and gas chromatography-mass spectrometry (GC-MS) shows that the pesticide residue detection results of the first and second grosvenor momordica fruit extracts 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 the error term meshes of the 400-item grosvenor momordica fruit by a liquid chromatography and gas chromatography-mass spectrometry (GC-MS), wherein the pesticide residue detection result of the first grosvenor momordica fruit extract obtained by the method is that dimethomorph 0.23mg/kg, iprodione 0.11mg/kg, oxadixyl 0.05mg/kg, propamocarb and propamocarb salt 0.27mg/kg, and other items are lower than the quantitative limit or are not detected;
The pesticide residue detection result of the second Siraitia grosvenorii extract in this example is that dimethomorph 0.12mg/kg, iprodione 0.06mg/kg, oxadixyl 0.05mg/kg, propamocarb and propamocarb salt 0.22mg/kg, other items lower than quantitative limit or not detected
Comparative example 2
The pulping and extracting in the step (2) is changed into the steps of feeding the de-enzymed fresh fruits into a pulping machine at a feeding speed of 1 ton/hour, simultaneously feeding hot water at 70 ℃ at a flow speed of 3 tons/hour, pulping and extracting to obtain a pulping extract, collecting extraction residues for later use, and operating the rest steps in accordance with the embodiment 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 fructus momordicae extract obtained in the example is 49.06 percent, the content of mogroside V in the second fructus momordicae extract is 60.18 percent, the content of mogroside V in the second fructus momordicae extract is 23.60 percent, the content of mogroside in the second fructus momordicae extract is 29.25 percent, and the total yield of mogroside V is 84.66 percent and the total yield of mogroside is 85.25 percent through calculation.
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 rest of the grosvenor momordica fruit with a size of error term meshes by a liquid chromatography and gas chromatography-mass spectrometry (GC-MS) to obtain the first grosvenor momordica fruit extract with the methamidophos content of 0.11mg/kg and the second grosvenor momordica fruit extract with the methamidophos content of 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 the mogroside V is 91.50 percent and the yield of the 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) The fresh fruit de-enzyming method comprises the steps of immersing complete fresh fructus momordicae in hot water containing a slow-release oxidant, fully immersing, and taking out to obtain de-enzyming fresh fruit, wherein the slow-release oxidant is obtained by compounding polyvinyl alcohol and polyhydroxy fatty acid encapsulated superfine calcium peroxide;
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;
(2) Pulping and extracting, namely adding the de-enzymed fresh fruits into a pulping machine, and simultaneously, introducing hot water, pulping and extracting to obtain a pulping extracting solution, collecting extraction residues for later use, wherein the temperature of the hot water is 105-110 ℃, and the dosage of the hot water is 1-1.5 times of the weight of the fresh fruits of the momordica grosvenori;
(3) Countercurrent extraction, namely countercurrent extracting the pulped extraction slag to obtain countercurrent extraction liquid;
(4) Horizontal screw centrifugation, namely mixing beating extracting solution and countercurrent extracting solution, and filtering by using a horizontal screw centrifuge to obtain horizontal screw centrifugal filtrate;
(5) Disc centrifugation, namely filtering the horizontal spiral centrifugal filtrate by using a disc centrifuge to obtain disc centrifugal filtrate;
(6) Ceramic membrane filtration, namely filtering the disc-type centrifugal filtrate by using a ceramic membrane to obtain ceramic membrane filtrate;
(7) Sterilizing the ceramic membrane filtrate with UHT equipment, and cooling to obtain sterilized material;
(8) Macroporous resin adsorption, namely passing the sterilized material through a macroporous adsorption resin column;
(9) Removing impurities, namely after macroporous resin adsorption is finished, washing a resin column by dilute alkali liquor, and washing the resin column to be neutral by pure water;
(10) Gradient eluting with aqueous medium ethanol, subjecting to macroporous adsorbent resin column eluting, adding modified activated carbon into the medium ethanol eluate, heating, stirring, filtering, concentrating, and drying to obtain first fructus Siraitiae Grosvenorii extract;
(11) Gradient eluting II, namely eluting the macroporous adsorption resin column by using a high-ethanol aqueous solution, adding modified activated carbon into the high-ethanol eluent, heating, stirring, filtering, concentrating and drying to obtain a second fructus momordicae extract;
The modified activated carbon is prepared by the steps of uniformly mixing the activated carbon and a modifier, 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 washing with water to neutrality, wherein the modifier is a mixture of KOH and potassium permanganate according to a mass ratio of 10-15:1;
The modifier is 0.5-0.8 times of the active carbon by mass, and the powder is particles with the size of 0.5-2 mm;
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 120-180 kHz.
2. The co-production method of the superfine calcium peroxide according to claim 1, wherein the particle size of the superfine calcium peroxide is 50-200nm, the preparation method of the superfine calcium peroxide comprises the following steps of dissolving calcium chloride in an alcohol-water solution, filtering, adding a surfactant and ammonia water into filtrate, slowly dropwise adding hydrogen peroxide under stirring, dropwise adding NaOH and/or KOH solution to generate white precipitate, filtering, washing, and vacuum freeze-drying to obtain the superfine calcium peroxide.
3. The co-production method according to claim 2, wherein the molar ratio of calcium chloride to hydrogen peroxide is 3-5:1, the mass concentration of hydrogen peroxide is 20-35 wt%, the surfactant is selected from PEG with the number average molecular weight of 1000-2000, the addition amount of the surfactant is 3-6wt% of the mass of calcium chloride, the mass concentration of ammonia water is 20-30%, the addition amount of ammonia water is adjusted to be 9-10, the slow dropwise adding of hydrogen peroxide is completed within 1-2h, the mass concentration of NaOH/KOH solution is 1-5wt%, the addition amount is adjusted to be 11-12, the alcohol-water solution is obtained by mixing ethanol and deionized water, and the volume content of ethanol is 30-50%.
4. The co-production method according to claim 2, wherein the ultrasonic agitation is carried out at 30-60kHz and 600-1000rpm, and the freeze-drying is carried out at-60 ℃ to-30 ℃ and 10-100Pa for 5-10 hours.
5. The co-production method according to claim 1, wherein in the step (1), the temperature of the hot water is 50-60 ℃, the soaking time is 3-6 hours, and the mass concentration of the slow-release oxidant is 2-3wt%.
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;
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 the specific surface area of the activated carbon before modification is 400-800 m 2/g, and the specific surface area of the activated carbon after modification is 2000-m 2/g.
8. The co-production method according to claim 1, wherein in the step (10), the volume percentage concentration of the aqueous medium ethanol solution is 30-45 vol%, the dosage of the medium ethanol is 3-5BV, and the stirring time is 1-3 hours;
In the step (11), the volume percentage concentration of the high-grade ethanol is 50-75 vol%, and the dosage of the high-grade ethanol is 1-3BV.
9. The co-production method according to claim 1, wherein in the step (10), the amount of the modified activated carbon is 0.05-0.1 wt% of the weight of fresh fruits of momordica grosvenori, and the heating temperature is 60-90 ℃.
10. The co-production method according to claim 1, wherein in the step (11), the amount of the modified activated carbon is 0.02-0.05wt% based on the weight of fresh fruits of momordica grosvenori, the heating temperature is 60-90 ℃, and the stirring time is 1-3 hours.
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