CN113142538A

CN113142538A - Zero calorie sugar for improving sweetness of mogroside and preparation method thereof

Info

Publication number: CN113142538A
Application number: CN202110410802.XA
Authority: CN
Inventors: 刘庚贵; 黄华学; 黄�俊; 曾润清; 何安乐
Original assignee: Hunan Huacheng Biotech Inc
Current assignee: Hunan Huacheng Biotech Inc
Priority date: 2021-04-16
Filing date: 2021-04-16
Publication date: 2021-07-23
Anticipated expiration: 2041-04-16
Also published as: CN113142538B

Abstract

The invention relates to zero-calorie sugar for improving sweetness of mogroside and a preparation method thereof, wherein the zero-calorie sugar comprises the following components in percentage by mass: 0.1-3.0 wt% of mogroside V, 0.007-0.9 wt% of other mogrosides, and 94.00-99.90 wt% of erythritol. The zero calorie sugar is obtained by compounding a momordica grosvenori high-power sweetener and erythritol and performing boiling granulation, wherein the momordica grosvenori high-power sweetener is obtained by physically refining momordica grosvenori sweet glycosides serving as a raw material sequentially through a polar macroporous adsorption resin column, a high-specific surface activity macroporous adsorption resin column and a small-pore reverse phase gel column. According to the invention, phenolic acid, pigment and bitter components existing in the mogroside are removed through a specific process, the relative proportion of main sweet saponin components in the mogroside is regulated, the relative content is further regulated through an erythritol compounding technology, and the sweetness performance of the mogroside is synergized synergistically, so that the sweetness performance of the mogroside is remarkably improved.

Description

Zero calorie sugar for improving sweetness of mogroside and preparation method thereof

Technical Field

The invention relates to the technical field of plant extraction and separation and the field of sweetener compounding, in particular to a zero calorie sugar for improving the sweet taste performance of mogroside and a preparation method thereof.

Background

The invention mainly relates to mogroside and erythritol.

Mogroside I, Grosvenor momordica

Mogroside is prepared from fresh mature fruit of Momordica grosvenori Swingle of Cucurbitaceae by saccharifying and ripening, and separating and extracting. The most common mogroside sold in the market is V50 standard, and the content of mogroside V is about 50%. The main process comprises the steps of saccharifying fresh momordica grosvenori, curing, crushing, extracting with water, filtering, micro-filtering and clarifying by a ceramic membrane, carrying out chromatography by broad-spectrum macroporous absorption resin, decoloring by ion exchange resin, desalting, carrying out vacuum concentration, carrying out spray drying and the like. Mogroside is the variety with the best taste in all natural sweet substances, is the closest to sucrose, has the remarkable advantages of fresh sweet taste, high sweetness and low calorie of sucrose, does not change blood pressure and blood sugar, does not cause decayed teeth, does not cause obesity, is particularly suitable for people with diabetes, hypertension, obesity and inapplicable sugar, is also an ideal sugar substitute for healthy people, does not have the lasting after-bitterness and metal taste of stevioside, and does not have the bitter before-sweetness taste of rubusoside, so the mogroside is most easily accepted by all people, and is a special part; however, the defects of sweetness performance such as taste, sweetness multiple, sweetness duration and the like of the commercially available mogroside limit the wide use of the grosvenor momordica extract.

Although most of substances originally existing in fresh momordica grosvenori, such as glucose, fructose, protein, amino acid, flavone, pigment and the like, are removed by separating and purifying the mogroside, partial acid phenol substances still remain, particularly the mogroside is most common in the market, and a V50 product which is widely applied still has certain defects in the aspect of sweet taste: (1) the taste is slightly bitter and astringent after the mouth is taken, and disappears in about 8 seconds; (2) the sweetness multiple is high and is 160-200 times of that of cane sugar, the dosage is not easy to control, and the sweet potato is not suitable to be directly used as a sweet substitute; (3) the sweet taste is lasting, and the duration time is about 45 seconds. In contrast, the taste of sucrose is a sweet taste without bitterness, reaches a sweetness peak in about 2 seconds, and disappears in about 5 seconds, which is currently the most desirable sweet taste. Therefore, improving the sweetness of mogroside to approach the taste of sucrose has been a technical problem that those skilled in the art would expect to solve.

Factors influencing the taste and the mouthfeel of the mogroside are manifold, and documents report that bitter saponins, mogroside IIE, mogroside III and the like exist in the grosvenor momordica, and the 2 components generally exist in the grosvenor momordica harvested in winter, and are mixed into fruits in autumn in the production process, so that the finished product mogroside has slightly bitter taste in the mouth; the inventor of the application finds that phenolic acid, pigment and the like existing in fresh momordica grosvenori can also influence the taste and the mouthfeel of the mogroside in long-term scientific research and production practice, and the pure white mogroside has the best taste and mouthfeel on the premise that the product does not contain bitter saponin, namely the fresh sweet taste of sucrose; the inventor of the application also finds that if foreign matters introduced by decoloring of the ion exchange resin are not completely removed in the production process, the taste and the mouthfeel of the mogroside are greatly influenced, and although a desalting step exists in the production process of the mogroside, some foreign matters are not clear and cannot be completely removed.

Therefore, the preparation method removes phenolic acid, pigment, bitter and astringent components in the mogroside, foreign impurities generated by decoloration of ion exchange resin and other substances with undefined structures, and adjusts the relative proportion of main sweet saponin components, thereby improving the taste of the mogroside, reducing the sweetness multiple, shortening the sweetness duration time, preparing a sweet substitute, i.e. the mogroside, which has the fresh and cool sweetness like sucrose, achieves the sweetness multiple suitable for direct use, has the sweetness duration time close to that of the sucrose, is easy to be accepted by consumers, is the key of the mogroside towards terminal application products, is the problem which needs to be solved urgently in the mogroside industrialization, and is also the key technical problem which needs to be solved for further popularization and application of the mogroside.

II, erythritol

Erythritol is a natural substance used as bulk sweetenerHas been widely used. It is a four-carbon sugar alcohol with a molecular formula of C₄H₁₀O₄. Is white crystalline powder, has refreshing sweet taste, is not easy to absorb moisture, is stable at high temperature, is stable in a wide pH range, has mild cool feeling when dissolved in the mouth, and is suitable for various foods.

1. Characteristics of

Erythritol is white crystal, has sweetness about 70% of that of sucrose, and has cool feeling. Zero heat. Is soluble in water (37%, 25 deg.C), has low solubility (compared with sucrose), is not degraded by enzyme, can only be excreted from blood to urine through kidney (easy to be absorbed by small intestine), and is not involved in sugar metabolism and blood sugar change, so it is suitable for diabetic patients. It is not fermented in colon, and can avoid gastrointestinal discomfort. It does not cause dental caries. Erythritol has high stability: the product is stable to acid and heat, has high acid and alkali resistance, can not be decomposed and changed at 160 ℃, can not be discolored due to Maillard reaction, and is particularly suitable for processing food with strict requirements on color and luster. Erythritol has an endothermic effect when dissolved in water, and the heat of dissolution is only 97.4KJ/KG, which is higher than both glucose and sorbitol, and has a cooling feeling when eaten. Erythritol is very easy to crystallize, but does not absorb moisture in an environment with 90% humidity, and is easy to crush to obtain a powdery product, and the powdery product can be used on the surface of food to prevent the food from absorbing moisture and deteriorating.

2. Function(s)

(1) Zero heat: erythritol is the only zero calorie sugar alcohol. Because of its small molecular weight, it is easy to be absorbed by human body, and at the same time, only a small amount of erythritol absorbed by human body can be fed into human large intestine and fermented by microorganism. Most erythritol enters the blood circulation, but the human body lacks enzymes capable of metabolizing erythritol, and therefore erythritol entering the blood cannot be digested and degraded, and can be discharged from urine only through the kidneys. Such erythritol has a low-calorie character and is a natural zero-calorie bulk sweetener.

(2) High tolerance: the human body has a tolerance to erythritol of 0.8 g per kg body weight, which is the highest among sugar alcohols. The main reason is that erythritol has small molecular weight and less absorption and is mainly discharged through urine, so that diarrhea caused by a hypertonic phenomenon is avoided, and an flatulence phenomenon caused by intestinal bacterial fermentation is avoided.

(3) Anti-caries property: oral bacteria, especially streptococcus aureus, cannot utilize and ferment erythritol, so that acidic substances cannot be generated to damage teeth, and dental caries is induced.

(4) Promoting the proliferation of bifidobacteria: the utilization of erythritol by bacteria in the field shows that erythritol has obvious proliferation effect on bifidobacteria in intestinal tract.

At present, the research on the momordica grosvenori extract, particularly the momordica grosvenori glycoside, which is a representative of the momordica grosvenori extract, is more in China, and mainly relates to an extraction and separation process of the momordica grosvenori glycoside; the research on the compound sweetener added with the mogroside is also more, and the mogroside is mainly compounded with sugar alcohol, other plant extracts and the like to form the sweetener with the lower sweetness multiple. The literature and patent reports on the improvement of the sweetness performance of mogroside mainly develop from two aspects: firstly, removing the bitter taste accompanied with the mogroside; and secondly, sweet fillers such as sugar alcohol and the like are added to dilute the bad taste. At the present stage, a research object mostly uses fresh momordica grosvenori as a starting raw material, targets are directed to separate and prepare high-purity momordica grosvenori sweet glycosides, or various types of simple compounding are carried out, no commercially available momordica grosvenori sweet glycoside V50 standard is used as the starting raw material, phenolic acid, pigment, bitter ingredients and foreign impurities generated by decoloring ion exchange resin in the momordica grosvenori sweet glycosides are removed through a process technology, the relative proportion of main sweet saponin ingredients is adjusted, pure-taste momordica grosvenori sweet glycosides with good taste and mouthfeel and 55-70% of momordica grosvenori glycoside V content are obtained, the taste and mouthfeel of the momordica grosvenori sweet glycosides are improved by adding compounding substances in a synergistic manner, the sweetness is doubled, the sweetness duration time is shortened, and therefore the prepared momordica grosvenori sweet glycosides have the taste and the sweetness which are 1-10 times that of sucrose; report of arhat fructose with sweet taste duration less than or equal to 10 seconds.

The prior published technical content and solutions about improving the sweetness performance of mogroside are as follows:

1. removing bitter taste associated with mogroside.

CN201811397385.4 discloses a method for separating mogroside V from fructus momordicae, which comprises the steps of adding water into fructus momordicae, pulping, sequentially carrying out plant enzyme enzymolysis and biological enzyme enzymolysis, collecting enzymolysis liquid, carrying out yeast fermentation after enzyme deactivation, purifying by composite anion and cation exchange resin, concentrating and drying to obtain the mogroside V. The product prepared by the preparation method is snow white, has no bitter taste, little solvent residue, no pesticide residue and stable product quality, and the obtained mogroside V is more than 60 percent and the total glycoside is more than 90 percent.

The method only uses anion-cation exchange resin for purification, only uses chemical exchange adsorption, does not have a special macroporous adsorption resin step, can not obtain snow-white mogroside, and still has a certain amount of phenolic acid residue; foreign substances remain, and the alleged no bitter taste cannot be realized; this technique does not result in mogroside V greater than 60%.

Cn201711064166.x discloses a purification method of flavored mogroside V, which comprises the following steps: (1) polyamide adsorption: dissolving the crude extract of mogroside with water, loading onto polyamide resin chromatographic column, and collecting effluent; (2) alkali adjustment and ultrafiltration: adjusting the pH value of the effluent to 8-10, standing, coarsely filtering, ultrafiltering, and collecting the filtrate; (3) ion exchange adsorption: sequentially loading the filtrate on a cation exchange resin column and an anion exchange resin column, and collecting effluent liquid; (4) and (3) decoloring and drying: and (3) passing the effluent through a decolorizing resin column, collecting the effluent, concentrating, and performing spray drying to obtain the flavored mogroside V. In the product obtained by the method, the mass content of mogroside V is more than 60%, the yield is more than or equal to 90%, the mass content of the afterbitter source substance is less than 0.06%, the removal rate is more than 99.5%, no afterbitter exists, and the product is fresh and cool in taste, pure in taste, good in uniformity and stable in property; the method is simple, has strong operability and is suitable for industrial production.

The method adopts anion-cation exchange resin for purification and decoloration resin for decoloration, and the basic principle is that foreign substances are introduced and remain, bitter and astringent components cannot be completely removed, the relative proportion of main sweet saponin cannot be adjusted, and no afterbitterness exists, but the bitter and astringent taste in the mouth is still obvious and cannot be removed, so that the optimal proportion of the sweet components cannot be achieved.

CN201610860141.X discloses a method for extracting mogroside without bitter taste, which comprises the following steps: 1) dissolving mogroside in water, loading onto DM130 macroporous resin, eluting with water to colorless, eluting with ethanol, collecting ethanol eluate, and recovering ethanol from the eluate to obtain extract; 2) dissolving the extract in water, loading onto D101+ macroporous resin, eluting with water, collecting eluate, concentrating, and drying. Compared with the prior art, the extracted mogrosides of the invention do not contain bitter substances, and have pure sweet taste and no bitter taste.

The method only uses broad-spectrum macroporous adsorption resin for refining, and the 2 kinds of resin have strong adsorption capacity on the mogroside, the flavone, the pigment and the like, can not realize separation, can not remove phenolic acid substances in the mogroside, can not decolor, and can not adjust the relative proportion of main sweet saponin.

CN201610860168.9 discloses a preparation method of a debitterized fructus momordicae extract, which comprises the following steps: 1) adding fructus Siraitiae Grosvenorii into ethanol for extraction, filtering the extractive solution, and recovering ethanol from the filtrate to obtain extract A; 2) dissolving the extract A in water, adding AB-8 macroporous resin, eluting with water to colorless, eluting with ethanol, collecting ethanol eluate, and recovering ethanol from the eluate to obtain extract B; 3) dissolving the extract B in water, loading onto D101+ macroporous resin, eluting with water, collecting eluate, concentrating, and drying. Compared with the prior art, the fructus momordicae extract prepared by the invention does not contain bitter substances, has pure sweet taste and does not have bitter taste.

CN200710003364.5 discloses a preparation method of a decolored and debitterized fructus momordicae extract, which is characterized in that: using water as solvent, adopting reflux extraction method, filtering and concentrating the extract, decolorizing with decolorizing resin, eluting with ethanol, deodorizing with deodorizing agent, recovering ethanol, concentrating, spray drying, and pulverizing to obtain decolorized and debitterized fructus Siraitiae Grosvenorii extract, which is white and crystalline powder with pure sweet taste and no traditional Chinese medicine taste or afterbitterness, wherein the content of mogroside by weight is above 90%.

The method only uses decolorizing resin for refining, and cannot prepare 90% mogroside V; and the decolorizing resin is eluted by ethanol, all components are eluted together, no refining step is actually carried out, mogroside flows out in the feeding process without being exchanged and adsorbed by the decolorizing resin, the pigment is exchanged and adsorbed, and the ethanol eluting part is the components such as the pigment, impurities and the like. The method cannot debitterize mogroside.

2. Adding sweet bulking agent such as sugar alcohol to dilute the taste.

CN202010579810.2 discloses a sweet taste composition capable of replacing sucrose and a preparation method thereof, wherein the food additive composition is composed of the following raw materials in parts by weight: specially-made mixed powder material 0.01-20; 0.01-40 parts of special xylitol; 25-99.96 parts of erythritol; 0.01-5 parts of L-arabinose; mogroside 0.01-10; the specially prepared mixed powder comprises the following components: 2-5 parts of pawpaw, 6-12 parts of coix seed, 3-12 parts of konjak, 2-5 parts of purple perilla, 1-3 parts of hawthorn, 3-12 parts of rhizoma polygonati, 4-8 parts of mulberry leaf, 4-8 parts of platycodon grandiflorum, 2-5 parts of medlar, 6-12 parts of cassia seed, 1-3 parts of lophatherum gracile, 2-4 parts of chrysanthemum and 2-8 parts of liquorice.

CN201910623559.2 discloses an edible sweet granule for diabetics and a preparation method thereof, wherein the sweet granule is composed of the following raw materials in parts by weight: 0.1-0.5 part of momordica grosvenori extract, 0.3-0.8 part of lithocarpus litseifolius extract, 60-80 parts of konjac refined powder and 10-30 parts of arabinose; the mogroside V content in the momordica grosvenori extract is not less than 90%, the lithocarpus litseifolius extract comprises 30-40% of phlorizin and 60-70% of trilobatin in percentage by weight, and the glucomannan content in the konjac refined powder is more than 90%.

CN201711165148.0 discloses a preparation method of a compound sweetener, the compound sweetener has soft front taste, clean back taste and no foreign taste, and has a taste similar to that of cane sugar. The preparation method is characterized in that trehalose, arabinose (component A), mogroside, L-glycine and derivatives thereof (component B) and other natural sweet tastes (component C) are uniformly mixed according to a certain formula proportion, or are dissolved in water according to the formula proportion, and then the product is prepared by concentration crystallization or spray drying.

The application of the mogroside compound sweetener is that sugar alcohol, arabinose and one or more substances are added on the basis of the mogroside and the compound sweetener is prepared by simple processes such as mixing, drying, or granulating, drying and the like, and only relates to simple proportioning and does not relate to the improvement of the taste and the mouthfeel of the mogroside from the process technology.

The above technology and compounding method for improving the sweetness of mogroside are not ideal, and are specifically shown in the following steps: (1) the chemical exchange adsorption of the ion exchange resin is taken as a key for separation and purification, foreign substances are introduced, and the final product has residues and has no corresponding removal step or incomplete desalination to cause the bitter taste of the mogroside product; (2) broad-spectrum macroporous adsorption resin is taken as a key for separation and purification, and mogroside, phenolic acid, pigment and bitter components are adsorbed and desorbed together and cannot be effectively separated, so that the taste and mouthfeel are not improved; (3) the broad-spectrum macroporous adsorption resin and ion exchange resin separation and purification technology can not prepare pure white momordica glycosides with removed phenolic acid, pigment and bitter taste, and the currently marketed momordica glycosides are all similar white to milk powder white, and the taste and mouthfeel need to be further improved, which is a market certificate; (4) the process technology of adjusting the relative proportion of the main sweet saponin components is not available, the optimal relative proportion of the main sweet components cannot be maintained, and the optimal mouthfeel can be obtained through the synergistic effect; (5) sugar alcohol, arabinose and the like are added to compound a low-power sweet substance, the mixture ratio is simple, the sweetness and the bitter taste are simply diluted, the quantity of each sweet component is changed, the taste and the mouthfeel of the mogroside are not improved from the aspect of material basis, the sweet performance advantage of the mogroside cannot be highlighted, and the taste and the mouthfeel are further improved.

The applicant prepared a high-power sweetener for improving the taste and the mouthfeel of mogroside and a preparation method thereof in the previous patent application CN202110264251.0, so that impurities affecting the taste such as acid phenol and pigment can be effectively removed, the taste of the mogroside high-power sweetener product is improved, the sweet duration time is shortened, and meanwhile, the active ingredient mogroside V is basically not lost. Compared with the high-purity mogroside serving as a sweetening agent on the market, the taste is obviously improved. However, the sweetness performance, especially the aftertaste, is still severe. However, the high-potency sweetener still has long sweetness duration, and the taste and flavor are improved compared with the conventional high-purity mogroside sweetener on the market, but the taste and flavor are not satisfactory. Moreover, the high-power sweetener is inconvenient to use, reaches 300 times of 220 times of sweetness due to high sweetness, can be directly used only by diluting with a large factor when being used, is low in cost, is more popular in the market at present, is close to sucrose in sweetness factor, can be directly eaten in a mode similar to sucrose, and is more popular in actual sale with common consumers although the product has high premium. Therefore, the development of a low-intensity sweetener which can be directly used has good commercial prospect.

Disclosure of Invention

The technical problem to be solved by the invention is to overcome the defects and provide zero calorie sugar for improving the sweet taste performance of mogroside and a preparation method thereof, wherein the commercial mogroside V50 specification is used as a raw material, an ion exchange resin refining method which is difficult to completely remove and has an influence on the taste and the mouthfeel is not needed, but a pure physical adsorption separation and purification method is adopted to remove phenolic acid, pigment and bitter taste components existing in the mogroside, and foreign impurities and other unknown substances generated by the decoloration of the ion exchange resin in the traditional process, and the relative proportions of main sweet saponins, such as mogroside IV, mogroside V, 11-O-mogroside V, siamenoside I and mogroside VI, are adjusted by the process technology and the addition of specific food additives with certain biological activity and sweet taste performance, so that the components reach the optimal proportion of the mouthfeel, therefore, the sweetness of the mogroside is obviously improved, and the prepared mogroside has excellent taste, fresh and sweet taste like cane sugar, no slightly bitter taste in the mouth and sweetness which is 1-10 times that of the cane sugar; the duration of sweet taste is less than or equal to 10 seconds. The main factors of the sweetness multiple and the sweetness duration of the mogroside are determined by the inherent physicochemical properties of the mogroside, and the mogroside belongs to saponin substances with natural triterpene high sweetness. But the sweetness multiple and the sweetness duration are influenced by some phenolic acid, pigment and impurities which are introduced by decoloring ion exchange resin and other substances with undefined structures and are accompanied with the mogroside and originally exist in the grosvenor momordica on one hand, and on the other hand, the sweetness multiple and the sweetness duration of the mogroside can be obviously improved through the further influence of the compounding of specific non-sugar substances and the synergistic action of the two. According to the invention, the mogroside high-power sweetener and the erythritol which are subjected to special treatment are compounded, and the low-power compound grosvenor momordica zero calorie sugar is finally obtained through a boiling granulation process, so that the duration time of sweet taste can be greatly reduced, the taste and flavor are close to those of cane sugar, and meanwhile, the flowability of the mogroside powder is improved through the combination with the erythritol and the boiling granulation process, and hardening is reduced. The Hanguo compound zero calorie sugar provided by the invention is an ideal low-power sweetener for replacing cane sugar.

The purpose of the invention is realized by the following technical scheme:

the zero calorie sugar for improving the sweet taste performance of mogroside is characterized by comprising the following components in percentage by mass: 0.1-3.0 wt% of mogroside V, 0.007-0.9 wt% of other mogrosides, and 94.00-99.90 wt% of erythritol.

The other mogrosides include mogroside IV, 11-O-mogroside V, siamenoside I, and mogroside VI.

Further, the zero calorie sugar for improving the sweet taste performance of the mogroside comprises the following components in mass content: 0.1-2.0 wt% of mogroside V, 0.02-0.35 wt% of other mogrosides, 97.00-99.90 wt% of erythritol; furthermore, the zero calorie sugar for improving the sweet taste performance of the mogroside comprises the following components in mass content: 0.13-0.93 wt% of mogroside V, 0.02-0.15 wt% of other mogrosides, and 99.71-98.53 wt% of erythritol.

In the zero calorie sugar, the mass content of mogroside V is 5-7 times of that of other mogrosides; preferably, the mass content of mogroside V is 6-6.5 times of that of other mogrosides.

Furthermore, the zero calorie sugar for improving the sweet taste performance of the mogroside is obtained by compounding a mogroside high-power sweetener and erythritol and performing boiling granulation, wherein the mogroside high-power sweetener is obtained by physically refining the raw material, which sequentially passes through a polar macroporous adsorption resin column, a high-specific surface activity macroporous adsorption resin column and a small-pore reverse gel column.

The solid dried by the momordica grosvenori high-intensity sweetener comprises the following components: 55-70 wt% of mogroside V, 1.5-4 wt% of mogroside IV, 3-10 wt% of 11-O-mogroside V, 0.5-1.8 wt% of siamenoside, 0.4-1.5 wt% of mogroside VI, less than 0.2 wt% of acid phenolic substances and less than 0.2 wt% of pigment substances; when the high intensity sweetener is a concentrated solution, the above ingredients and their amounts refer to the ingredients and amounts of the product that is substantially free of water when the concentrated solution is dried (e.g., vacuum dried, spray dried, freeze dried).

Preferably, the dried solid of the momordica grosvenori high-intensity sweetener comprises the following components: 2.3-3.0 wt% of mogroside IV, 58-65 wt% of mogroside V, 5-7 wt% of 11-O-mogroside V, 0.9-1.3 wt% of siamenoside, 0.7-1.1 wt% of mogroside VI, less than 0.15 wt% of acid phenolic substances and less than 0.1 wt% of pigment substances.

The Lo Han Guo high intensity sweetener may be in the form of a solid (powder, granules, chunks), or a concentrated solution. The solid (the water content is less than or equal to 2%) of the dried fructus momordicae high-power sweetener can contain the components with the mass content.

The mogroside is preferably mogroside V50, wherein the product with mogroside V content of 42-55% is a conventional commercially available product or powder of fructus Siraitiae Grosvenorii extract obtained by conventional method.

The acid phenolic substances are fructus momordicae polyphenol, kaempferol, amino acid, phenolic acid with unknown structure and the like. Due to the preparation process, especially in the sweetener which is obtained by adopting ion exchange resin and takes mogroside V as the main sweet component, especially in the most common product of mogroside V50 on the market, the acid phenol accounts for 2-5 wt% of mogroside, and the taste of the high-power sweetener which takes mogroside V as the main sweet substance is seriously influenced.

The polar macroporous adsorption resin is selected from at least one of ADS-7, LX-8, LX-17 and LX-38; the macroporous adsorption resin with high specific surface activity is selected from at least one of LX-68G, XDA-7, XDA-200B, LX-10G, LSA-10 and LSA-5B; the small-pore reverse phase GEL column has a particle size of 75-150 μm series, and is one or a mixture of polystyrene type (such as GEL CHP 20SS, GEL CHP 2MG) or methacrylate type (such as GEL CHP 20SS, GEL CHP 2 MG).

Preferably, the macroporous adsorption resin with high specific surface activity is modified by a cross-linking agent after being subjected to chloromethylation, wherein the cross-linking agent is selected from polyamine; more preferably, the polyamine is at least one selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and polyethyleneimine. The dosage of the cross-linking agent is 8-15 wt% of the macroporous absorption resin with high specific surface activity.

The specific modification method comprises the steps of adding swelling agent into chloromethylated macroporous adsorption resin with high specific surface activity for swelling, adding catalyst and polyamine cross-linking agent, heating and stirring for reaction for 10-20h, filtering, washing and drying to obtain the cross-linked and modified macroporous adsorption resin with high specific surface activity.

The swelling agent is selected from nitrobenzene, dimethyl sulfoxide, toluene and dichloromethane, and dimethyl sulfoxide is preferably used as the swelling agent for toxicity. The swelling time is not 8-12 h. Too long or too short swelling time is not favorable for crosslinking modification of the macroporous adsorption resin with high specific surface activity.

Chloromethylation of macroporous adsorbent resin is well known in the art, and specifically, the macroporous adsorbent resin is added into a carbon tetrachloride solution of 1, 4-dichloromethoxybutane, after standing and swelling, anhydrous zinc chloride is added, stirring is carried out for 12-18h at 50-60 ℃, ethanol and deionized water are used for washing until no precipitate is formed after a silver nitrate solution is added, and chloromethylation of the macroporous adsorbent resin is completed.

The macroporous adsorbent resin with high specific surface activity modified by the cross-linking agent reduces the pore passage of the resin, further increases the specific surface area, allows pigment and phenolic acid molecules to enter the pore passage more easily, has relatively large molecular weight of saponins, and is not easy to diffuse in the pore passage of the resin, thereby realizing better separation. After the macroporous adsorption resin with high specific surface activity is subjected to crosslinking reduction, the saturated adsorption rate of the adsorbent to the mogroside is only 2-3%, and the loss of the saponin can be basically avoided.

The inventor finds that the conventional mogroside V50 product in the market contains a certain amount of phenolic acid, such as momordica grosvenori polyphenol, kaempferol, amino acid, phenolic acid with unknown structure and the like, and also contains part of pigment, particularly has a certain number of unknown components in the V50 specification obtained by ion exchange resin, due to the limitations of the extraction process and the production cost; the momordica grosvenori product has different varieties and maturity of momordica grosvenori and different processing technologies, the total amount of phenolic acid is about 2-5 wt%, although the content of phenolic acid is not large, the phenolic acid is a main factor influencing the taste of momordica grosvenori glycoside V50, and meanwhile, the pigment not only influences the color of the product, but also has certain influence on the taste. Therefore, the invention adopts a physical adsorption mode, does not introduce other impurities, and uses polar macroporous adsorption resin and macroporous adsorption resin with high specific surface activity to carry out specific and selective adsorption on phenolic acid and pigment. The inventor also finds that the modification of the macroporous adsorption resin with high specific surface activity can not only effectively remove phenolic acid in the raw material, but also basically does not adsorb mogroside V which is a main component. The economy of the process of the invention is ensured. Because if the loss of mogroside V is large even if impurities such as phenolic acid are finally removed, it is not paid. Therefore, the invention aims to solve the main technical problem that the loss of mogroside V is as little as possible while removing impurities and improving the mouthfeel of mogroside V50.

The grosvenor momordica high-power sweetening agent obtained by the specific method removes most of impurities such as acid phenol and the like, improves the taste and flavor of mogroside, is compounded with erythritol, and is subjected to boiling granulation to obtain grosvenor momordica zero calorie sugar, the sweet taste duration is further reduced to less than or equal to 10 seconds, and the grosvenor momordica zero calorie sugar obtained by the boiling granulation is a crystal with good fluidity, is not easy to absorb moisture, and can be stored for a long time without affecting the taste and flavor. Is a zero calorie sugar which is suitable for being directly sold on the market to replace cane sugar.

The invention also provides a preparation method of the zero calorie sugar for improving the sweet taste performance of the mogroside, which comprises the following steps:

(1) preparing mogroside powder into a mogroside aqueous solution, passing through a polar macroporous adsorption resin column, feeding, then using a purified water washing resin column, and collecting a feeding effluent liquid and a water washing liquid;

(2) and (2) enabling the combined effluent liquid and water washing liquid obtained in the step (1) to pass through a macroporous adsorption resin column with high specific surface activity, feeding the mixture, then using a purified water washing resin column, and collecting the feed effluent liquid and the water washing liquid.

(3) Enabling the combined effluent liquid in the step (2) and the water washing liquid to pass through a small-hole reverse phase gel column, and collecting a feeding effluent liquid; after feeding, washing the small-hole reversed-phase gel column with water, and collecting water washing liquid; then carrying out gradient elution by using an alcohol-water mixed solution, and collecting high-concentration alcohol-water eluent; mixing the feed effluent, water eluate and high-concentration alcohol-water eluate, and vacuum-reducing to remove alcohol smell to obtain refined solution;

(4) passing the refined liquid obtained in the step (3) through a physical adsorption chromatographic column, feeding, washing with water, and combining a feeding effluent liquid and a washing liquid;

(5) and (4) concentrating the combined liquid of the feed effluent liquid and the water washing liquid in the step (4) under vacuum and reduced pressure to obtain a concentrated solution, compounding the concentrated solution and erythritol, and performing boiling granulation to obtain the zero calorie sugar of which the sweet taste performance of the mogroside is improved.

Preferably, in the step (1), the mogroside refers to a commercially available mogroside V50 specification, wherein the mogroside V content is 42.0-55.0%, and the color is similar to white to milk powder white; and preparing a mogroside powder aqueous solution to obtain an aqueous solution with a solid content of 3-8 Brix.

Preferably, in the step (1), the addition amount of the polar macroporous adsorption resin is 5-10 times of the weight of the mogroside; the adding amount of the high specific surface active resin in the step (2) is 1-3 times of the weight of the mogroside; and (4) adding 15-30 times of the weight of the mogroside into the microporous reverse phase gel in the step (3).

Preferably, in the step (1) and the step (2), the collected parts are a feed effluent liquid and a water washing liquid, and the adding amount of the water washing liquid is 1-2 times of the mass of the polar macroporous adsorption resin and the mass of the macroporous adsorption resin with high specific surface activity respectively; in the step (3), the water consumption for washing the micropore reverse phase gel column is 1.5-2.5 times of that of the micropore reverse phase gel, and in the gradient elution of the alcohol-water mixed solvent, the use amount of the alcohol-water mixed solvent is 2.5-4 times of that of the micropore reverse phase gel. The lower alcohol is at least one of methanol, ethanol and propanol, preferably ethanol.

Preferably, the high specific surface active macroporous adsorption resin in the step (2) is modified by crosslinking. And (3) performing column loading and elution by using pure water in the step (2), wherein the pure water has no desorption effect on the mogrosides and can cause certain loss of the mogrosides. After the macroporous adsorption resin with high specific surface activity is subjected to crosslinking modification, on one hand, the adsorption of acidic phenol impurities can be enhanced, on the other hand, the yield of the mogroside can be improved, and the loss rate of the mogroside is reduced.

More preferably, the gradient elution in the step (3) is performed by eluting with a low-concentration alcohol-water mixed solvent with a volume concentration of 5-10% and then eluting with a high-concentration alcohol-water mixed solvent with a volume concentration of 40-60%; further preferably, the volume ratio of the low-concentration alcohol-water mixed solvent to the high-concentration alcohol-water mixed solvent is 1-2: 1-2. Preferably 1: 1-1.2.

Preferably, in the step (4), the physical adsorption chromatography column filler is one of granular activated carbon and nylon activated carbon or any combination thereof; the adding amount of the active carbon chromatographic column filler is 0.5-1.5 times of the weight of the mogroside V50; the amount of the water washing water is 3-6 times of the weight of the mogroside.

Preferably, in step (5), the vacuum concentration is carried out under reduced pressure at a temperature of 60-65 ℃ under a vacuum degree of-0.05 to-0.1 MPa, which is well known in the art. Vacuum concentrating under reduced pressure to 20-25% solid content.

And (5) putting erythritol into a fluidized bed, keeping the erythritol in a boiling state, heating, taking the concentrated solution containing the mogroside as a spraying solution, uniformly mixing, and carrying out boiling granulation to obtain crystals, thus obtaining the zero calorie sugar of which the sweet taste performance of the mogroside is improved.

The spraying liquid is a concentrated liquid, preferably, the spraying liquid is prepared by compounding the concentrated liquid and a part of erythritol, and the rest erythritol is put into a fluidized bed. Preferably, the erythritol used to formulate the spray-on with the concentrate comprises 3-8%, preferably 4-6% of the total erythritol; the ratio of the concentrate to erythritol is not particularly limited as long as it satisfies the content of mogroside V in the final product Lo Han Kuo zero calorie sugar in the range of 0.1 to 2.0 wt%, and preferably, the ratio of the concentrate to erythritol is such that the content of mogroside V in the final product Lo Han Kuo zero calorie sugar is in the range of 0.13 to 0.93 wt%.

The process parameters for boiling granulation are well known in the art. In one embodiment of the invention, the conditions of the boiling granulation process are that the temperature is 70-75 ℃ and the spraying speed of the spraying liquid is 7-10 kg/h.

Preferably, in step (5), the dried product of the concentrated solution, i.e. the lo han guo high intensity sweetener, mainly consists of: 55-70 wt% of mogroside V, 1.5-4 wt% of mogroside IV, 3-10 wt% of 11-O-mogroside V, 0.5-1.8 wt% of siamenoside, 0.4-1.5 wt% of mogroside VI, less than 0.2 wt% of acid phenolic substances and less than 0.2 wt% of pigment substances; preferably, the momordica grosvenori high intensity sweetener comprises the following components: 2.3-3.0 wt% of mogroside IV, 58-65 wt% of mogroside V, 5-7 wt% of 11-O-mogroside V, 0.9-1.3 wt% of siamenoside, 0.7-1.1 wt% of mogroside VI, less than 0.15 wt% of acid phenolic substances and less than 0.1 wt% of pigment substances.

The invention adopts a pure physical adsorption separation and purification method, does not introduce foreign impurities and has obvious effect. The macroporous adsorption resin is combined according to a certain sequence, so that most of phenolic acid, pigment and other impurities in the mogroside product are removed, the mogroside is basically not adsorbed, the separation is realized, the taste is improved, the mogroside V serving as a main component is basically not lost, and the retention rate is over 90 percent; the small-pore reverse phase gel has a molecular separation function, can carry out primary separation on substances with different molecular weights and molecular structures, has certain adsorption on phenolic acid, pigment, foreign substances generated by decolorization of the original process ion exchange resin and mogroside components, can realize separation of mogroside and impurities from the molecular structures and the molecular weights by combining water washing in a gradient elution mode through aqueous ethanol with different concentrations, and can adjust the composition of main saponin sweet components, thereby obviously improving the taste and the mouthfeel of the mogroside; the activated carbon chromatography can adsorb phenolic acid, pigment, foreign substances, peculiar smell and the like generated by the decolorization of the original process ion exchange resin, basically has no adsorption to mogroside, and can clarify pure mogroside solution by a simple mode. Through the technical combination, phenolic acid, pigment and bitter components existing in the mogroside and foreign impurities generated by decoloring of ion exchange resin in the traditional process are removed, the relative proportion of main saponin sweet components is adjusted, and the sweet taste performance of the mogroside is improved in the technical aspect. The pure mogroside prepared by the process technology has the key index component of higher mogroside V content, namely, 220-280 times of cane sugar sweetness, and the sweet taste performance at the time is not optimal. The applicant finds that the taste of the filling type sweetener erythritol and the taste of the pure mogroside have a synergistic effect through research, the taste of the mogroside is obviously improved, the sweetness multiple is reduced, the sweetness duration time is shortened, the anti-dental caries effect is realized, and zero calorie is realized, so that the sweetness performance and the bioactivity of the mogroside are fully exerted. The relative contents of main sweet components in the mogroside, such as mogroside IV, mogroside V, 11-O-mogroside V, siamenoside I and mogroside VI, can be further adjusted through the erythritol, so that the components can reach the proportion of the most suitable taste, and the sweet taste performance of the mogroside is further improved from the new idea of compounding.

The pure mogroside is powder, has poor fluidity and certain hygroscopicity. Through boiling granulation, the powder form of the mogroside can be changed, the fluidity is improved, the hardening is reduced, and then the mogroside zero calorie sugar with improved sweetness of the mogroside is prepared by drying. In a preferred boiling granulation process, a small amount of erythritol and the mogroside-containing concentrated solution which is treated and has most of impurities such as acid phenol, pigment and the like removed are prepared into a spraying liquid, so that the spraying liquid contains a certain amount of erythritol, and the obtained momordica grosvenori zero-calorie sugar is obtained through boiling granulation, so that the product quality is more uniform and stable, namely the product is a product with higher mogroside content, the moisture absorption rate is low, the storage stability of the product is ensured, and the use of consumers is facilitated.

The invention has the beneficial effects that:

(1) the invention provides a method for improving sweetness of mogroside. Phenolic acid, pigment and bitter components existing in the mogroside are removed through a specific process, foreign substances introduced by decoloration of ion exchange resin in a commercial mogroside V product are removed, the relative proportion of main sweet saponin components in the mogroside is adjusted, the relative content is further adjusted through an erythritol compounding technology, and the sweetness performance of the mogroside is synergized synergistically, so that the sweetness performance of the mogroside is remarkably improved.

(2) According to the invention, the relative proportion of main sweet saponin components in the mogroside, namely mogroside IV, mogroside V, 11-O-mogroside V, siamenoside I and mogroside VI, is adjusted through special resin according to a specific separation and purification sequence, so that the taste and mouthfeel of the mogroside are obviously improved.

(3) The method provides a key technology of chemical exchange adsorption for replacing ion exchange resin decolorization with pure physical separation and purification, solves the decolorization effect which cannot be achieved by secondary ion exchange resin decolorization under the conditions of no introduction of foreign substances and chemical exchange reaction, and prepares the pure white momordica grosvenori zero calorie sugar.

(4) In the preferred technical scheme of the invention, the macroporous adsorption resin with high specific surface activity is subjected to crosslinking modification, so that the pore passages of the resin are reduced, the specific surface area is further increased, the pigment and phenolic acid molecules are easier to enter the pore passages, and the saponins have relatively large molecular weights and are difficult to diffuse in the pore passages of the resin, so that the better separation can be realized, and the retention rate of mogroside V is further increased.

(5) The boiling granulation method improves the fluidity of the mogroside powder and reduces hardening. The erythritol is divided into two parts, wherein a small amount of erythritol and the concentrated solution are prepared into the spraying liquid, and then the spraying liquid and the residual erythritol are subjected to boiling granulation together, so that a product with more uniform and stable quality is obtained, even the product with higher mogroside V content can be kept without absorbing moisture for a long time, and the product is convenient for consumers to purchase and use.

(6) The invention provides a sweetener, namely momordica grosvenori zero calorie sugar, for improving the sweet taste performance of momordica grosvenori sweet glycosides. The main sweet taste components are as follows: 0.1-2.0 wt% of mogroside V, 0.02-0.35 wt% of other mogrosides, 97.00-99.90 wt% of erythritol; the color is pure white, and the character is crystallization; the sweetness is 1-10 times of that of cane sugar; the duration of the sweet taste is less than or equal to 10 seconds; sweetness performance: sucrose is fresh and cool, has pure sweet taste, no bitter taste and good taste, and is basically the same as sucrose.

Detailed Description

The present invention will be further described with reference to the following examples.

The mogroside V50 used in the embodiment of the invention is produced by Hunan Huacheng biological resource GmbH, and the preparation process comprises the following steps: saccharifying fresh fructus Siraitiae Grosvenorii, crushing, extracting with water, filtering, clarifying with ceramic membrane microfiltration, performing broad-spectrum macroporous adsorbent resin chromatography, decolorizing with ion exchange resin, desalting, vacuum concentrating, and spray drying to obtain the final product), wherein the content of mogroside IV is 3.72%, the content of mogroside V is 51.62%, the content of 11-O-mogroside V is 5.96%, the content of siamenoside I is 0.95%, and the content of mogroside VI is 0.92%; the total amount of momordica grosvenori polyphenol, kaempferol, amino acid, phenolic acid with unknown structure and the like (measured by a UV method) is 3.25 percent.

Erythritol is purchased from bowling bio-incorporated; the used purified water is prepared by secondary pure water equipment used in a production workshop, and the used macroporous adsorption resin, macroporous reverse phase gel, activated carbon filler for chromatography and raw and auxiliary materials are all obtained by conventional commercial approaches if no special description is provided.

In the embodiment of the invention, the taste, the sweetness multiple and the sweetness duration are measured by perception; the contents of mogroside IV, mogroside V, 11-O-mogroside V, siamenoside I and mogroside VI are determined by High Performance Liquid Chromatography (HPLC), and the content of phenolic acid is determined by Folin phenol method and ultraviolet-visible spectrophotometry (UV), and the absorbance at 765nm is determined.

Preparation example 1 Cross-linking modification of XDA-200B resin

Adding 1kg of XDA-200B resin, 3.5L of BCMB and 12L of carbon tetrachloride into a reaction kettle with stirring, standing and swelling for 10h, adding 0.2kg of anhydrous zinc chloride, reacting for 12h under the condition of stirring at 60 ℃, washing with anhydrous ethanol and deionized water after the reaction is finished until no precipitate is generated after a nitrate solution is added, and obtaining the chloromethylated XDA-200B resin. Adding the chloromethylated XDA-200B resin into dehydrated 12L dimethyl sulfoxide to swell for 8h, slowly adding 0.2kg of anhydrous aluminum chloride, 0.1kg of anhydrous zinc chloride and 0.08kg of triethylenetetramine, heating to 50 ℃, reacting for 12h under stirring, filtering, washing with anhydrous ethanol and deionized water respectively until no precipitate is generated when a nitrate solution is added, placing the obtained resin into a forced air dryer, and performing vacuum drying at 60 ℃ overnight to obtain the crosslinked modified XDA-200B resin.

The pore size of the crosslink modified XDA-200B resin was tested to decrease from 150 to 90 angstroms.

Preparation example 2 Cross-linking modification of LSA-5B resin

Adding 1kg of LSA-5B resin, 3.5L of BCMB and 12L of carbon tetrachloride into a reaction kettle with stirring, standing and swelling for 10h, adding 0.2kg of anhydrous zinc chloride, reacting for 12h under the stirring condition at 60 ℃, washing with anhydrous ethanol and deionized water after the reaction is finished until no precipitate is generated after adding a nitrate solution, and obtaining the chloromethylated LSA-5B resin. Adding chloromethylated LSA-5B resin into dehydrated 12L dimethyl sulfoxide for swelling for 8h, slowly adding 0.2kg of anhydrous aluminum chloride, 0.1kg of anhydrous zinc chloride and 0.12k of ethylenediamine, heating to 50 ℃, reacting for 12h under stirring, filtering, washing with anhydrous ethanol and deionized water respectively until no precipitate is generated when a nitrate solution is added, placing the obtained resin in a forced air drier, and performing vacuum drying at 60 ℃ overnight to obtain the crosslinking modified LSA-5B resin.

The pore size of the cross-linked modified LSA-5B resin was tested to decrease from 130 angstroms to 80 angstroms.

Example 1

(1) 80kg of LX-17 resin is filled in a stainless steel chromatographic column in advance, and the resin is well treated by ethanol, 4 percent of sodium hydroxide aqueous solution and 4 percent of hydrochloric acid according to the standard procedure of regeneration treatment of macroporous adsorption resin for standby. Taking 10kg of mogroside V50 powder, adding 150L of purified water, stirring for dissolving, passing the dissolved solution through a chromatographic column filled with LX-17 resin, and collecting feed effluent; after feeding, adding 130L of purified water washing resin column, collecting water washing liquid, and combining the feeding effluent liquid and the water washing liquid.

(2) In advance in stainless steel chromatographic column filled with preparation 1 obtained crosslinked modified XDA-200B resin 18kg and ethanol, 4% sodium hydroxide aqueous solution, 4% hydrochloric acid according to macroporous adsorbent resin regeneration standard procedure processing for use. Passing the combined solution obtained in the step (1) through a chromatographic column filled with XDA-200B resin, and collecting feed effluent; after the feeding, the column was further subjected to 35L of a purified water-washed resin column to collect a water-washed liquid. The feed effluent and the aqueous wash are combined.

(3) 200kg of GEL CHP 20SS filler is filled in a stainless steel chromatographic column in advance, and the stainless steel chromatographic column is treated by ethanol and purified water for standby. Enabling the combined solution obtained in the step (2) to pass through a chromatographic column filled with small-hole reverse phase gel, and collecting a feed flow and a discharge liquid to obtain a feed liquid 1; after feeding, feeding into a 400L purified water washing column, and collecting water washing liquid to obtain feed liquid 2.

Then carrying out gradient elution by using ethanol-water solution: firstly, 300L of 8% ethanol-water solution with volume concentration is added, and effluent liquid is collected; and adding 350L of 40% ethanol, and collecting eluate to obtain feed liquid 3.

Mixing the feed liquids 1, 2 and 3 to obtain a mixed solution, performing vacuum concentration under reduced pressure at vacuum degree of-0.085 MPa and temperature of 63 deg.C, recovering ethanol until no alcohol smell exists, and concentrating to obtain refined solution.

(4) 9kg of granular activated carbon for chromatography is filled in a stainless steel chromatographic column in advance, and the granular activated carbon is treated by ethanol and purified water for later use. Passing the refined solution through a chromatographic column filled with granular activated carbon, and collecting feed effluent; after the feed was completed, the column was washed with 36L of purified water, and the water was collected. And (4) combining the feed effluent and the water washing liquid to obtain the pure mogroside solution.

(5) Concentrating the pure mogroside solution under vacuum degree of-0.085 MPa and temperature of 65 deg.C under reduced pressure to 20.1% solid content to obtain 37.0kg concentrated solution. Taking 4.4kg of erythritol, adding 20.0L of purified water, stirring and dissolving to obtain an erythritol solution; and then 1.0kg of concentrated solution is taken and mixed with the erythritol solution to obtain a compound solution as a spraying solution.

(6) Boiling and granulating. Firstly, putting 95.4kg of erythritol into a fluidized bed, and keeping a boiling state, a medium and high wind speed and a temperature of 72 ℃; secondly, spraying the compound liquid at a constant speed of 8.5kg per hour; ③ evenly mixing and drying to obtain 97.9kg of crystal, namely the momordica grosvenori zero calorie sugar.

Through detection, in the powdered product which is obtained by drying the concentrated solution obtained in the step (5) in the embodiment and is basically free of water, namely the high-power momordica grosvenori sweetener comprises 2.51% of mogroside IV, 63.75% of mogroside V, 6.65% of 11-O-mogroside V, 1.06% of siamenoside I and 0.92% of mogroside VI; the total amount of fructus Siraitiae Grosvenorii polyphenol, kaempferol, amino acids and phenolic acid with unknown structure is 0.04%, and the retention rate of mogroside V is 93.35%. .

Through detection, the fructus momordicae zero calorie sugar has good taste, is basically the same as sucrose, and has no slightly bitter taste; the sweetness is 1 time of that of cane sugar; sweetness duration 7 seconds; mogroside V content 0.13%, other mogrosides content 0.02%, erythritol content 99.71%.

Example 2

(1) The ADS-7 resin 100kg is loaded in the stainless steel chromatographic column in advance and processed by ethanol, 4% sodium hydroxide water solution and 4% hydrochloric acid according to the standard procedure of macroporous adsorbent resin regeneration treatment for standby. Taking 10kg of mogroside V50 powder, adding 200kg of purified water, stirring for dissolving, passing the dissolved solution through a chromatographic column filled with ADS-7 resin, and collecting feed effluent; after the feeding, the resin column was further subjected to 180L of purified water to collect the water-washed liquid. The feed effluent and the aqueous wash are combined.

(2) 25kg of the modified LSA-5B resin obtained in preparation example 2 was previously loaded into a stainless steel column and treated with ethanol, 4% aqueous sodium hydroxide solution and 4% hydrochloric acid according to the standard procedure for regeneration of macroporous adsorbent resins. Passing the combined solution obtained in the step (1) through a chromatographic column filled with LSA-5B resin, and collecting a feed effluent; after the feeding, 50L of purified water washing resin column is fed, and the water washing liquid is collected. The feed effluent and the aqueous wash are combined.

(3) 240kg of methacrylate type GEL CHP 2MG filler is filled in a stainless steel chromatographic column in advance, and is treated by ethanol and purified water for standby. Passing the decolorized solution through a chromatographic column filled with small-pore reverse-phase gel, and collecting feed effluent to obtain feed liquid 1; after feeding, feeding the mixture into a 500L purified water washing column, and collecting water washing liquid to obtain feed liquid 2.

Then carrying out gradient elution by using aqueous ethanol: firstly, 400L of 7% ethanol with concentration is added, and effluent liquid is collected; then 500L of 42% ethanol with concentration is added, and the eluent in the section is collected to obtain feed liquid 3.

Mixing the feed liquids 1, 2 and 3 to obtain a mixed solution, performing vacuum concentration under reduced pressure at vacuum degree of-0.085 MPa and temperature of 61 deg.C, recovering ethanol until no alcohol smell exists, and concentrating to obtain refined solution.

(4) 12kg of polyamide active carbon for chromatography is filled in a stainless steel chromatographic column in advance, and the polyamide active carbon is well treated by ethanol and purified water for later use. Passing 270L of refined solution through a chromatographic column filled with nylon activated carbon, and collecting feed effluent; after the feed was completed, 50L of purified water was further introduced into the column, and the water was collected. And (4) combining the feed effluent and the water washing liquid to obtain the pure mogroside solution.

(5) Compounding and adjusting the sweet taste performance; concentrating the mogroside solution under vacuum at-0.085 MPa and 62 deg.C to 22.6% solid content to obtain 36.4kg concentrated solution. Taking 7.0kg of erythritol, adding 15.0L of purified water, stirring and dissolving to obtain an erythritol solution; and then 12.9kg of concentrated solution is taken and mixed with the erythritol solution to obtain a compound solution as a spraying solution.

(6) Boiling and granulating. Firstly, putting 90.3kg of erythritol into a fluidized bed, and keeping a boiling state, a medium and high wind speed and a temperature of 75 ℃; secondly, spraying the compound liquid at a constant speed of 9.0kg per hour; ③ mixing evenly to obtain 98.3kg of crystal to obtain the product of the momordica grosvenori zero calorie sugar.

Through detection, in a powdery product which is obtained by drying the concentrated solution obtained in the step (5) of the embodiment and is basically free of water, namely the momordica grosvenori high-power sweetener, the content of mogroside IV is 2.36%, the content of mogroside V is 60.41%, the content of 11-O-mogroside V is 6.62%, the content of siamenoside I is 1.06%, and the content of mogroside VI is 1.01%; the total amount of fructus Siraitiae Grosvenorii polyphenol, kaempferol, amino acids and phenolic acid with unknown structure is 0.07%, and the retention rate of mogroside V is 92.18%.

Through detection, the fructus momordicae zero calorie sugar has good taste, is basically the same as sucrose, and has no slightly bitter taste; the sweetness is about 11 times of that of cane sugar; sweetness duration 10 seconds; mogroside V content is 1.64%, other mogrosides content is 0.26%, erythritol content is 97.61%.

Example 3

The other operations and conditions were the same as in example 1 except that 37.0kg of the concentrated solution was obtained in step (5). Taking 5.0kg of erythritol, adding 20.0L of purified water, stirring and dissolving to obtain an erythritol solution; and then 7.4kg of concentrated solution is taken and mixed with the erythritol solution to obtain a compound solution as a spraying solution.

(6) Boiling and granulating. Putting 92.5kg of erythritol into a fluidized bed, and keeping a boiling state, a medium and high wind speed and a temperature of 72 ℃; secondly, spraying the compound liquid at a constant speed of 8.5kg per hour; ③ mixing evenly to obtain 98.4kg of crystal to obtain the product of the momordica grosvenori zero calorie sugar.

Through detection, the fructus momordicae zero calorie sugar has good taste, is basically the same as sucrose, and has no slightly bitter taste; the sweetness is 7 times of that of cane sugar; sweetness duration 9 seconds; mogroside V content 0.93%, other mogrosides content 0.15%, erythritol content 98.53%.

Example 4

The other operations and conditions were the same as in example 3 except that in step (5), 7.4kg of the concentrated solution was taken as a spraying solution;

(6) boiling and granulating. Putting 97.5kg of erythritol into a fluidized bed, and keeping a boiling state, a medium and high wind speed and a temperature of 72 ℃; secondly, spraying the compound liquid at a constant speed of 8.5kg per hour; ③ mixing evenly to obtain 98.4kg of crystal to obtain the product of the momordica grosvenori zero calorie sugar.

Example 5

The other operations and conditions were the same as in example 2 except that in step (5), 12.9kg of the concentrated solution was taken as a spraying solution;

(6) boiling and granulating. Putting 97.3kg of erythritol into a fluidized bed, and keeping a boiling state, a medium and high wind speed and a temperature of 75 ℃; secondly, spraying the compound liquid at a constant speed of 9.0kg per hour; ③ mixing evenly to obtain 98.3kg of crystal to obtain the product of the momordica grosvenori zero calorie sugar.

Example 6

The other operations and conditions were the same as in example 1 except that the XDA-200B resin modified by crosslinking in step (2) was replaced with an XDA-200B resin which had not been modified.

Through detection, the white powdery product fructus momordicae high-power sweetener obtained by drying the concentrated solution obtained in the step (5) contains 2.43% of mogroside IV, 61.84% of mogroside V, 5.45% of 11-O-mogroside V, 1.13% of siamenoside I and 0.95% of mogroside VI; the total amount of fructus Siraitiae Grosvenorii polyphenol, kaempferol, amino acids and unknown structure phenolic acid is 0.15%, and the retention rate of mogroside V is 88.93%.

Finally, boiling and granulating to obtain a product of the momordica grosvenori zero calorie sugar, and detecting, the momordica grosvenori zero calorie sugar obtained in the embodiment has good taste, is basically the same as cane sugar, and has no slightly bitter taste; the sweetness is about 1 time of that of cane sugar; sweetness duration 7 seconds; mogroside V content 0.126%, other mogrosides 0.022%, erythritol content 99.81%.

Comparative example 1

The mogroside with the V50 specification produced by Hunan Huacheng biological resource GmbH is a high-power sweetener. I.e., the feedstock processed by the above examples of the present invention.

Comparative example 2

(1) Taking 0.1kg of mogroside with the specification of V50 produced by Hunan Huacheng biological resource GmbH, as a high-power sweetener, taking 1.8kg of erythritol, adding 20.0L of purified water, stirring, and dissolving to obtain a compound liquid of V50 and erythritol as a spraying liquid;

(2) boiling and granulating. Firstly, 39.8 kg of erythritol is put into a fluidized bed, and the boiling state and medium and high wind speed are kept at the temperature of 72 ℃; secondly, spraying the compound liquid at a constant speed of 8.5kg per hour; ③ evenly mixing and drying to obtain 40.4kg of crystal, namely the momordica grosvenori zero calorie sugar.

Through detection, the fructus momordicae zero calorie sugar has good taste, is basically the same as sucrose, and has no slightly bitter taste; the sweetness is 1 time of that of cane sugar; sweetness duration 7 seconds; mogroside V content 0.12%, other mogrosides content 0.02%, erythritol content 99.58%.

Application example 1

The characteristics of the sweeteners obtained in the embodiment and the proportion are evaluated by adopting 20 blind test sets, and the specific method is as follows:

1. screening and training of sensory analysts

Sensory evaluators were screened according to the regulations of GB/T16291.2-2010, and after training for taste sensitivity, 20 sensory evaluators (male and female halves) were finally screened to constitute a sensory evaluation panel.

2. Duration of sweetness: the test person is asked to taste an aqueous solution of the compound sweetener of the present invention diluted to a sweetness level close to 5 wt% sucrose solution. The time to the disappearance of sweetness perceived by the subjects was recorded from the time the panelists began to drink, excluding those who tasted 5 wt% sucrose for a sweetness duration that deviated from 5 seconds for more than 1 second, i.e., excluding those who tasted 5 wt% sucrose/brown sugar solutions for sweetness durations less than 4 seconds and greater than 6 seconds. The resulting average is the sweetness duration of the sweetener of the present invention.

3. Subjective evaluation of mouthfeel:

the sensory analysts restricted the diet, especially the food that severely affected the taste sensation, within 1h before the start of the assessment experiment. For different taste tests, 12 most suitable sensory analysts in 20 of each group were selected for sensory evaluation of the compound sweetener solution. The smell and the taste of the solution of the sweetening agent are comprehensively graded and evaluated, the value is 1 to 10, 5 wt% of cane sugar is used as a reference, the satisfaction degree is the highest and is 10, 12 questionnaire testers take the number of the questionnaire testers every time, the highest value and the lowest value are removed, and finally the overall average value is obtained.

The test samples are divided into a product group and a control group, the product group is the fructus momordicae zero calorie sugar obtained by the embodiment and the comparative example of the invention, the sweetness of the added block is close to that of a 5 wt% sucrose solution, 10mL of the solution to be evaluated is put in a disposable paper cup and is held in the mouth by sensory evaluation personnel, the solution is discharged after staying for a plurality of seconds, the evaluation time interval is 20min, and the evaluation result is the average value of the scores of the 10 evaluation personnel. The sensory rating scale for the control group was 10 point full.

The test results are shown in table 1 below:

TABLE 1

As can be seen from the data in Table 1, according to the invention, by a specific preparation process, impurities which affect the taste and flavor of the sweetener, such as acid phenol and the like remained in the mogroside V50 product are effectively removed, meanwhile, the mogroside V as a main component is not basically lost, and the retention rate is basically more than 90%. Compounding the concentrated solution with erythritol, and finally preparing white crystal particles of the momordica grosvenori zero calorie sugar through boiling granulation; the sweetness is 1-15 times of that of cane sugar/brown sugar; the duration of the sweet taste is less than or equal to 10 seconds, and the sweet taste performance is as follows: fresh and cool, pure sweet taste, no bitter taste, good taste and basically the same as sucrose. The preparation method is simple, has low cost, can effectively improve the taste and flavor of the mogroside, and enlarges the audience of the mogroside product.

In addition, by comparing examples 3 and 4 and comparing examples 2 and 5, it can be seen that erythritol is completely fed into a fluidized bed as a solid in the boiling granulation process, or a small amount of erythritol is compounded with a concentrate containing mogroside as a spraying liquid, and then the erythritol is subjected to boiling granulation together with other erythritol, so that the taste and flavor of the final product, namely the momordica grosvenori zero calorie sugar, are not affected.

As can be seen from the comparative example 1, the momordica grosvenori zero calorie sugar provided by the invention greatly improves the sweet taste performance of the momordica grosvenori glycoside V50 as a sweetener; comparative example 2 was prepared by directly compounding untreated mogroside V50 with erythritol to give a mogroside V content similar to that of example 1, but with a much less bitter taste than example 1. The processing technology of the mogroside V50 is successful, the taste and flavor are improved, the loss rate of the mogroside V is within an acceptable range, but the taste is obviously improved, the product sale is facilitated, and the popularization of the mogroside in consumers is expanded.

Application example 2

Visually comparing the momordica grosvenori zero calorie sugars of examples 1-6 as follows: visual inspection of the appearance was rated on the following scale: grade A: the granularity is consistent, the spherical shape is realized, and the fluidity is good; grade B: the granularity has the deviation which can be identified by naked eyes, and is spherical, ellipsoidal and general in fluidity; grade C: the particle size is obviously different with naked eyes, and the particles are in various irregular shapes and have poor fluidity.

The evaluation of the moisture bearing rate is carried out by accurately weighing a certain mass (m)₀) The sweeteners of the examples and comparative examples were placed in a petri dish at 25 ℃ in a thermostat at 65 RH% and after 12h removed, the mass (m) was measured₁). Moisture absorption rate (%) m according to the following formula₁-m₀/m₀X 100%. The results are calculated as shown in table 2 below:

TABLE 2

Momordica grosvenori sugar without calorie	Appearance (visual inspection)	Rate of wetting
			Example 1	A	2.17％
Example 2	A	2.63％
			Example 3	A	2.54％
Example 4	A	2.86％
			Example 5	A	5.24％
Example 6	A	2.21％

As can be seen from the data in Table 2, the Momordica grosvenori zero calorie sugar prepared by the embodiment of the invention has the advantages of uniform particle size, good fluidity and low moisture content. Moreover, by comparing the example 3 with the example 4 and comparing the example 2 with the example 5, it is believed that the addition of a small amount of erythritol in the spraying liquid is more beneficial to the uniform stability of the product, and particularly for the product with higher mogroside content, the lower moisture exposure rate can be ensured, the market sale is more convenient, and the product price is increased.

Claims

1. The zero calorie sugar for improving the sweet taste performance of mogroside is characterized by comprising the following components in percentage by mass: 0.1-3.0 wt% of mogroside V, 0.007-0.9 wt% of other mogrosides, and 94.00-99.90 wt% of erythritol.

2. The zero-calorie sugar according to claim 1, characterized by comprising the following components in mass content: 0.1-2.0 wt% of mogroside V, 0.02-0.35 wt% of other mogrosides, 97.00-99.90 wt% of erythritol; preferably, the zero calorie sugar comprises the following components in percentage by mass: 0.13-0.93 wt% of mogroside V, 0.02-0.15 wt% of other mogrosides, and 99.71-98.53 wt% of erythritol.

3. The zero-calorie sugar according to claim 1 or 2, wherein the zero-calorie sugar for improving the sweetness of mogroside is prepared by compounding a mogroside high-power sweetener and erythritol and performing boiling granulation, wherein the mogroside high-power sweetener is prepared by taking mogroside as a raw material and sequentially passing through a polar macroporous adsorption resin column, a high specific surface activity macroporous adsorption resin column and a small-pore reverse-phase gel column and performing physical refining.

4. The zero calorie sugar according to claim 3, wherein the dried solid of Lo Han Guo high intensity sweetener comprises the following ingredients: 55-70 wt% of mogroside V, 1.5-4 wt% of mogroside IV, 3-10 wt% of 11-O-mogroside V, 0.5-1.8 wt% of siamenoside, 0.4-1.5 wt% of mogroside VI, less than 0.2 wt% of acid phenolic substances and less than 0.2 wt% of pigment substances;

5. The zero-calorie sugar according to claim 3, wherein the polar macroporous adsorbent resin is selected from at least one of ADS-7, LX-8, LX-17, LX-38; the macroporous adsorption resin with high specific surface activity is selected from at least one of LX-68G, XDA-7, XDA-200B, LX-10G, LSA-10 and LSA-5B; the small-pore reverse phase GEL column has a particle size of 75-150 μm series, and is one or a mixture of polystyrene type (such as GEL CHP 20SS, GEL CHP 2MG) or methacrylate type (such as GEL CHP 20SS, GEL CHP 2 MG).

6. The zero-calorie sugar according to claim 3, wherein the macroporous adsorbent resin with high specific surface activity is modified by a cross-linking agent after chloromethylation, wherein the cross-linking agent is selected from polyamine; the dosage of the cross-linking agent is 8-15 wt% of the macroporous absorption resin with high specific surface activity.

7. The method of preparing a zero calorie sugar for improving the sweetness of mogroside according to any one of claims 1-6, comprising the steps of:

8. The preparation method according to claim 7, wherein in the step (1), the mogroside is a commercially available mogroside V50 specification, wherein the mogroside V content is 42.0-55.0%; preparing a mogroside powder aqueous solution to obtain an aqueous solution with a solid content of 3-8 Brix; the addition amount of the polar macroporous adsorption resin is 5-10 times of the weight of the mogroside;

the adding amount of the high specific surface active resin in the step (2) is 1-3 times of the weight of the mogroside;

and (4) adding 15-30 times of the weight of the mogroside into the microporous reverse phase gel in the step (3).

In the step (1) and the step (2), the addition amount of the water washing liquid is 1-2 times of the mass of the polar macroporous adsorption resin and the mass of the macroporous adsorption resin with high specific surface activity respectively;

in the step (3), the water consumption for washing the micropore reverse phase gel column is 1.5-2.5 times of that of the micropore reverse phase gel, and in the gradient elution of the alcohol-water mixed solvent, the use amount of the alcohol-water mixed solvent is 2.5-4 times of that of the micropore reverse phase gel.

9. The method according to claim 7, wherein the gradient elution in the step (3) is performed by eluting with a low-concentration alcohol-water mixed solvent having a volume concentration of 5 to 10% and then with a high-concentration alcohol-water mixed solvent having a volume concentration of 40 to 60%; preferably, the volume ratio of the low-concentration alcohol-water mixed solvent to the high-concentration alcohol-water mixed solvent is 1-2: 1-2.

10. The preparation method according to claim 7, wherein the boiling granulation process in step (5) is that erythritol is put into a fluidized bed, the erythritol is kept in a boiling state, heating is carried out, the concentrated solution containing mogroside is used as a spraying solution, the concentrated solution is uniformly mixed, and crystallization is carried out through boiling granulation, so that the zero-calorie sugar with the sweet taste of mogroside improved is obtained;

preferably, the sprayed liquid is a concentrated liquid and a part of erythritol are compounded, and the rest erythritol is put into a fluidized bed; the erythritol used for preparing the spray solution with the concentrated solution accounts for 3-8%, preferably 4-6% of the total erythritol.