CN111153943A - Method for extracting stevioside by recrystallization method - Google Patents
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Abstract
A method for extracting stevioside by recrystallization comprises the following steps of raw material extraction, flocculation process, adsorption separation, concentration, crystallization, centrifugal separation, reverse osmosis concentration, recrystallization and post-treatment. In the stevioside disclosed by the invention, the stevioside is separated and purified by using a recrystallization method, and other impurities are removed by optimizing the process. The pure, high-content and safe stevioside product is obtained. The total glycoside content is higher than 99%, and the stevioside A content is higher than 98%.
Description
Technical Field
The invention relates to the technical field of food additive preparation, in particular to a method for extracting stevioside by a recrystallization method.
Background
Stevia rebaudiana (stevia rebaudiana) is also known as stevia rebaudiana (Bertoni) and Glycyrrhiza glabra, belongs to Compositae (Compositae), Stavida, and is native in subtropical areas of south America. Since 1976, China introduced stevia rebaudiana into Japan successively for successful test breeding by scientific research units such as Nanjing Zhongshan botanical garden and Chinese academy of agricultural sciences. Stevia rebaudiana contains 14 trace elements and 32 nutrient components, is not metabolized, accumulated, carcinogenic and toxic in the body, has safety approved by international FAO and WHO, American FAD and other organizations, and is an excellent sugar source and a good nutrient source.
Stevioside, a type of terpene glycosides with sweetness extracted from dried stevia leaves, mainly contains 8 kinds of glycosides with different sweetness. Stevioside has the characteristics of high sweetness (200 times of sucrose) and low calorie (only 1/300 of sucrose), does not cause people to be fat after long-term eating, is particularly suitable for patients with obesity, diabetes, hypertension, arteriosclerosis and dental caries, has stable physical and chemical properties and no fermentability, and can prolong the shelf life of stevioside products. Therefore, the sugar is increasingly attracting attention and attention of people, is widely applied to food and pharmaceutical industries, is known as the third natural sugar source after sucrose and beet sugar, and is the new sugar source with the greatest development prospect.
The research of the stevia sugar project mainly focuses on breeding of stevia leaves, decolorization and impurity removal of glycosides and recrystallization in three directions, at present, the highest glycoside content of products in national industrialized mass production can reach 85-90%, but the overall level is not optimistic, the glycoside content is below 80% and has a certain proportion higher than the light absorption, the common automation degree of stevia sugar processing enterprises is not high enough, the refining efficiency is low, and some low heteroglycosides cannot be separated, so that the phenomena of poor taste, yellow color, low additional value and the like hinder the further development of the stevia sugar industry in China, and a new technical scheme is specially provided for solving the problems.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a method for extracting stevioside by a recrystallization method, wherein the total glycoside content is higher than 99%, and the stevioside A content is higher than 98%.
A method for extracting stevioside by a recrystallization method comprises the following steps:
(1) raw material extraction: selecting high-quality stevia rebaudiana dry leaves by screening, performing 2-stage countercurrent extraction at the water temperature of 70-90 ℃, and feeding the extract into the next process;
(2) a flocculation procedure: placing the extractive solution in 40-50 deg.C water bath, stirring at constant temperature of 30-60rpm for 10-20min, adding flocculant, adjusting pH to 8-10, standing for 20-50min, and filtering to obtain clarified water extractive solution of stevia rebaudiana Bertoni; the flocculant comprises the following raw materials in parts by weight: 5-9 parts of chitosan, 15-25 parts of lignin, 10-18 parts of ammonium persulfate, 20-25 parts of polyaluminum ferric sulfate, 22-24 parts of aluminum citrate, 2-7 parts of magnesium sulfate, 1-4 parts of calcium chloride, 15-25 parts of polysilicate iron, 3-6 parts of sodium carboxymethylcellulose, 5-7 parts of activated carbon, 1-2 parts of bentonite and 2-4 parts of fly ash;
(3) adsorption separation: adsorbing the filtrate with macroporous adsorbent resin, stopping feeding, washing with water, desorbing with 50-85% ethanol, and collecting desorption solution;
(4) concentration and crystallization: concentrating the desorption solution under reduced pressure to 2-3 times of the feeding amount, adding 95% ethanol, and crystallizing for 5-12 hours;
(5) centrifugal separation: centrifuging the crystal material by using a centrifugal machine, and leaching by using 95% ethanol to obtain primary crystals;
(6) reverse osmosis concentration: dissolving the primary crystal obtained in the step (5) by using 95% ethanol, and performing reverse osmosis concentration treatment by using a ro membrane; then, desalting and decoloring are carried out: passing the concentrated solution through a cation column and an anion column, desalting and decolorizing, recovering solvent liquid, performing active carbon treatment, and spray drying to obtain a crude product;
(7) and (3) recrystallization: heating and dissolving the crude product and a methanol aqueous solution according to the mass ratio of 1:4-6, keeping the temperature to 15-25 ℃ after complete dissolution, stirring for 15-30 minutes every 1-3 hours, and separating the mixture liquid after 36-48 hours to obtain stevioside crystals;
(8) and (3) post-treatment: dissolving stevioside crystal in water, spray drying to obtain dried stevioside, and pulverizing.
Further, the chitosan in the step (2) is modified chitosan, and the preparation method of the modified chitosan comprises the following steps: soaking chitosan in 95% ethanol for 2-5h, transferring into a reactor, adding vanillin according to the mass ratio of vanillin to chitosan of 2-5: 1-4, stirring and refluxing in water bath with water as a solvent, adding a 10% diluted sodium hydroxide solution, filtering and cleaning, extracting with acetone, removing unreacted vanillin and other impurities, and drying to obtain vanillin modified chitosan.
Further, the preparation method of the polymeric aluminum ferric sulfate comprises the following specific steps: (1) putting 50-60g of ferrous sulfate heptahydrate into a beaker, adding distilled water and stirring to form uniform dilute pasty ferrous sulfate mixed solution; then 3-4mL of 98% concentrated H was added slowly with stirring2SO4Acidifying, and adjusting the pH of the mixed solution to 0.6-1.0; (2) adding 3.5-4.3g of sodium chlorate into the liquid prepared in the step (1) while stirring for oxidation; meanwhile, stirring at a low speed, and when uniform liquid is formed and no bubbles appear, stirring; (3) weighing aluminum sulfate according to the molar ratio of AL/Fe of 1: 11-1: 9, adding distilled water for dissolving, adding the aluminum sulfate into the ferrous sulfate mixed solution in the step (2) after dissolving, and simultaneously stirring uniformly at a low speed; (4) putting the ferrous sulfate mixed solution into a water bath kettle, and controlling the water bath temperature to be 60-80 ℃; starting the stirrer, and stirring at a low speed for 30-60 min; in the polymerization reaction process, H is added according to the proportion that the molar ratio of P/Fe is 0.1-0.33PO4As a stabilizer; (5) stirring for 20-45min, adding small amount of Na after the liquid is uniform2CO3Adjusting the alkalization degree to 0.3; (6) and after stirring is finished, taking out the product, standing for 24 hours to obtain the product, evaporating water, and drying to obtain the polymeric aluminum ferric sulfate.
Further, the flocculation procedure in the step (2): placing the extractive solution in 48 deg.C water bath, stirring at 50rpm for 16min, adding flocculant, adjusting pH to 9, standing for 35min, and filtering to obtain clarified water extractive solution of stevia rebaudiana Bertoni; the flocculant comprises the following raw materials in parts by weight: 5.2-6.3 parts of chitosan, 15.1-18.9 parts of lignin, 11-15.2 parts of ammonium persulfate, 21.3-23.2 parts of polymeric aluminum ferric sulfate, 22.4-23 parts of aluminum citrate, 3.1-5.2 parts of magnesium sulfate, 1.5-2.4 parts of calcium chloride, 16.4-19.5 parts of polysilicate iron, 3.5-4.4 parts of sodium carboxymethyl cellulose, 5.8-6.5 parts of activated carbon, 1.1-1.5 parts of bentonite and 2.3-2.9 parts of fly ash.
Further, in the step (7), recrystallization: heating the crude product and a methanol aqueous solution according to the mass ratio of 1:5 for dissolving, keeping the temperature to 18 ℃ after complete dissolution, stirring for 20 minutes every 2 hours, and separating the mixture liquid after 40 hours to obtain the stevioside crystal.
Further, the raw materials comprise the following components in parts by weight: 7.2-8.9 parts of chitosan, 21.2-24.7 parts of lignin, 15.3-17.5 parts of ammonium persulfate, 23.5-24.6 parts of polymeric aluminum ferric sulfate, 23.1-23.5 parts of aluminum citrate, 3.4-6 parts of magnesium sulfate, 3-3.5 parts of calcium chloride, 22-23.8 parts of polysilicate iron, 4.4-5.6 parts of sodium carboxymethyl cellulose, 6.1-6.5 parts of activated carbon, 1.3-1.85 parts of bentonite and 3-3.7 parts of fly ash.
Further, desorbing with 60% ethanol in step (3), and collecting the desorption solution.
Further, in the step (4), the stripping solution is concentrated under reduced pressure to 2.2 times of the feeding amount, and 95% ethanol is added for crystallization for 10 hours.
Further, the total glycoside content of the stevioside extracted by the method is higher than 99%, and the stevioside A content is higher than 98%.
A steviol glycoside prepared by the method.
The preparation method of the flocculant comprises the following steps: the composite material is prepared by uniformly mixing chitosan, lignin, ammonium persulfate, polymeric aluminum ferric sulfate, aluminum citrate, magnesium sulfate, calcium chloride, polysilicate iron, sodium carboxymethylcellulose, activated carbon, bentonite and fly ash.
In the stevioside disclosed by the invention, the stevioside is separated and purified by a recrystallization method, and other impurities are removed by optimizing the process. Obtaining the pure stevioside product with high content and safety. The total glycoside content is higher than 99%, and the stevioside A content is higher than 98%
The recrystallization method combines the flocculation process, and the obtained flocculant greatly improves the flocculation effect by optimizing the components and the content of the flocculant, and is easy to separate and less in total glycoside loss.
The method adopts chitosan, lignin and polymeric aluminum ferric sulfate as macromolecular flocculant to quickly connect a large amount of non-glycoside organic and inorganic impurities in the stevia rebaudiana water extract to form a flocculating constituent, then the flocculating constituent is settled, aluminum citrate forms a precipitate under an alkaline condition, and the flocculating constituent is matched with activated carbon, bentonite and fly ash, so that the flocculating constituent volume is increased, the flocculating constituent settling speed can also be increased, and the activated carbon, the bentonite and the fly ash can adsorb a large amount of chlorophyll, pigment, inorganic salt and other impurities in the stevia rebaudiana water extract in the settling process, thereby playing a role in decoloring and desalting, greatly improving the efficiency of the stevioside impurity removal process and shortening the production period of the impurity removal process.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A method for extracting stevioside by a recrystallization method comprises the following steps:
(1) raw material extraction: selecting high-quality stevia rebaudiana dry leaves by screening, performing 2-stage countercurrent extraction at the water temperature of 80 ℃, and feeding the extract into the next process;
(2) a flocculation procedure: placing the extractive solution in 42 deg.C water bath, stirring at constant temperature of 35rpm for 16min, adding flocculant, adjusting pH to 9, standing for 35min, and filtering to obtain clarified water extractive solution of stevia rebaudiana Bertoni;
the flocculant comprises the following raw materials in parts by weight: 6.6 parts of chitosan, 18.5 parts of lignin, 15.8 parts of ammonium persulfate, 23 parts of polymeric aluminum ferric sulfate, 23.5 parts of aluminum citrate, 4.2 parts of magnesium sulfate, 3.3 parts of calcium chloride, 18.2 parts of polysilicate iron, 3.6 parts of sodium carboxymethylcellulose, 5.5 parts of activated carbon, 1.45 parts of bentonite and 2.8 parts of fly ash.
The preparation method of the polymeric aluminum ferric sulfate comprises the following specific steps: (1) putting 55g of ferrous sulfate heptahydrate into a beaker, adding distilled water and stirring to form uniform dilute pasty ferrous sulfate mixed solution; then 3mL of 98% concentrated H were slowly added with stirring2SO4Acidifying, and adjusting the pH of the mixed solution to 1.0; (2) adding 3.8g of sodium chlorate into the liquid prepared in the step (1) while stirring for oxidation; meanwhile, stirring at a low speed, and when uniform liquid is formed and no bubbles appear, stirring; (3) weighing aluminum sulfate according to the molar ratio of AL/Fe of 1:11, adding distilled water for dissolving, adding the aluminum sulfate into the ferrous sulfate mixed solution in the step (2) after dissolving, and simultaneously stirring uniformly at a slow speed; (4)putting the ferrous sulfate mixed solution into a water bath kettle, and controlling the water bath temperature to be 75 ℃; starting a stirrer, and stirring for 45min at a low speed; during the polymerization, H is added in a proportion of 0.2 of the molar ratio of P/Fe3PO4As a stabilizer; (5) stirring for 28min, adding small amount of Na after the liquid is uniform2CO3Adjusting the alkalization degree to 0.3; (6) and after stirring is finished, taking out the product, standing for 24 hours to obtain the product, evaporating water, and drying to obtain the polymeric aluminum ferric sulfate.
(3) Adsorption separation: adsorbing the filtrate with macroporous adsorbent resin, stopping feeding, washing with water, desorbing with 50-85% ethanol, and collecting desorption solution;
(4) concentration and crystallization: concentrating the desorption solution under reduced pressure to 2.5 times of the feeding amount, adding 95% ethanol, and crystallizing for 8 hours;
(5) centrifugal separation: centrifuging the crystal material by using a centrifugal machine, and leaching by using 95% ethanol to obtain primary crystals;
(6) reverse osmosis concentration: dissolving the primary crystal obtained in the step (5) by using 95% ethanol, and performing reverse osmosis concentration treatment by using a ro membrane; then, desalting and decoloring are carried out: passing the concentrated solution through a cation column and an anion column, desalting and decolorizing, recovering solvent liquid, performing active carbon treatment, and spray drying to obtain a crude product;
(7) and (3) recrystallization: heating and dissolving the crude product and a methanol aqueous solution according to the mass ratio of 1:4.5, keeping the temperature to 18 ℃ after complete dissolution, stirring for 20 minutes every 2 hours, and separating the mixture liquid after 42 hours to obtain stevioside crystals;
(8) and (3) post-treatment: dissolving stevioside crystal in water, spray drying to obtain dried stevioside, and pulverizing.
Example 2
A method for extracting stevioside by a recrystallization method comprises the following steps:
(1) raw material extraction: selecting high-quality stevia rebaudiana dry leaves by screening, performing 2-stage countercurrent extraction at the water temperature of 75 ℃, and feeding the extract into the next process;
(2) a flocculation procedure: placing the extractive solution in water bath of 46 deg.C, stirring at 55rpm for 16min, adding flocculant, adjusting pH to 9, standing for 35min, and filtering to obtain clarified water extractive solution of stevia rebaudiana Bertoni;
the flocculant comprises the following raw materials in parts by weight: 7.3 parts of chitosan, 18.4 parts of lignin, 16.6 parts of ammonium persulfate, 23.5 parts of polymeric aluminum ferric sulfate, 23 parts of aluminum citrate, 3.5 parts of magnesium sulfate, 2.6 parts of calcium chloride, 19.6 parts of polysilicate iron, 3.9 parts of sodium carboxymethylcellulose, 6.6 parts of activated carbon, 1.25 parts of bentonite and 3.4 parts of fly ash.
The chitosan is modified chitosan, and the preparation method of the modified chitosan comprises the following steps: soaking chitosan in 95% ethanol for 3h, transferring into a reactor, adding vanillin according to the mass ratio of vanillin to chitosan of 2: 3, stirring and refluxing in water bath by taking water as a solvent, adding a 10% diluted sodium hydroxide solution, filtering and cleaning, extracting with acetone, removing unreacted vanillin and other impurities, and drying to obtain vanillin modified chitosan, wherein the water bath temperature is 70 ℃, the reaction time in the reactor is 16h, and the pH of the reaction solution is 5.
The preparation method of the polymeric aluminum ferric sulfate comprises the following specific steps: (1) putting 54g of ferrous sulfate heptahydrate into a beaker, adding distilled water and stirring to form uniform dilute pasty ferrous sulfate mixed solution; then 3.6mL of 98% concentrated H was added slowly with stirring2SO4Acidifying, and adjusting the pH of the mixed solution to 0.8; (2) adding 3.8g of sodium chlorate into the liquid prepared in the step (1) while stirring for oxidation; meanwhile, stirring at a low speed, and when uniform liquid is formed and no bubbles appear, stirring; (3) weighing aluminum sulfate according to the molar ratio of AL/Fe of 1:10, adding distilled water for dissolving, adding the aluminum sulfate into the ferrous sulfate mixed solution in the step (2) after dissolving, and simultaneously stirring uniformly at a slow speed; (4) putting the ferrous sulfate mixed solution into a water bath kettle, and controlling the water bath temperature to be 75 ℃; starting the stirrer, and stirring at a low speed for 40 min; during the polymerization, H is added in a proportion of 0.2 of the molar ratio of P/Fe3PO4As a stabilizer; (5) stirring for 30min, adding small amount of Na after the liquid is uniform2CO3Adjusting the alkalization degree to 0.3; (6) and after stirring is finished, taking out the product, standing for 24 hours to obtain the product, evaporating water, and drying to obtain the polymeric aluminum ferric sulfate.
(3) Adsorption separation: adsorbing the extract filtrate with macroporous adsorbent resin, stopping feeding, washing with water, desorbing with 55% ethanol, and collecting desorption solution;
(4) concentration and crystallization: concentrating the desorption solution under reduced pressure to 2.7 times of the feeding amount, adding 95% ethanol, and crystallizing for 8 hours;
(5) centrifugal separation: centrifuging the crystal material by using a centrifugal machine, and leaching by using 95% ethanol to obtain primary crystals;
(6) reverse osmosis concentration: dissolving the primary crystal obtained in the step (5) by using 95% ethanol, and performing reverse osmosis concentration treatment by using a ro membrane; then, desalting and decoloring are carried out: passing the concentrated solution through a cation column and an anion column, desalting and decolorizing, recovering solvent liquid, performing active carbon treatment, and spray drying to obtain a crude product;
(7) and (3) recrystallization: heating and dissolving the crude product and a methanol aqueous solution according to the mass ratio of 1:4.4, keeping the temperature to 19 ℃ after complete dissolution, stirring for 16 minutes every 2.5 hours, and separating the mixture liquid after 40 hours to obtain stevioside crystals;
(8) and (3) post-treatment: dissolving stevioside crystal in water, spray drying to obtain dried stevioside, and pulverizing.
Example 3
A method for extracting stevioside by a recrystallization method is characterized by comprising the following steps:
(1) raw material extraction: selecting high-quality stevia rebaudiana dry leaves by screening, performing 2-stage countercurrent extraction at the water temperature of 85 ℃, and feeding the extract into the next process;
(2) a flocculation procedure: placing the extractive solution in 41 deg.C water bath, stirring at 40rpm for 15min, adding flocculant, adjusting pH to 8.5, standing for 35min, and filtering to obtain clarified water extractive solution of stevia rebaudiana Bertoni;
the flocculant comprises the following raw materials in parts by weight: 6.5 parts of chitosan, 17 parts of lignin, 14.2 parts of ammonium persulfate, 23 parts of polymeric aluminum ferric sulfate, 21.3 parts of aluminum citrate, 3.6 parts of magnesium sulfate, 2.4 parts of calcium chloride, 18.1 parts of polysilicate iron, 4.3 parts of sodium carboxymethylcellulose, 6.2 parts of activated carbon, 1.44 parts of bentonite and 3.4 parts of fly ash.
The chitosan is modified chitosan, and the preparation method of the modified chitosan comprises the following steps: soaking chitosan in 95% ethanol for 4h, transferring into a reactor, adding vanillin according to the mass ratio of vanillin to chitosan of 3: 2, stirring and refluxing in water bath by using water as a solvent, adding a 10% diluted sodium hydroxide solution, filtering and cleaning, extracting with acetone, removing unreacted vanillin and other impurities, and drying to obtain vanillin modified chitosan. The temperature of the water bath is 75 ℃, the reaction time in the reactor is 16h, and the pH value of the reaction solution is 6.
The preparation method of the polymeric aluminum ferric sulfate comprises the following specific steps: (1) putting 55g of ferrous sulfate heptahydrate into a beaker, adding distilled water and stirring to form uniform dilute pasty ferrous sulfate mixed solution; then 3.2mL of 98% concentrated H was added slowly with stirring2SO4Acidifying, and adjusting the pH of the mixed solution to 0.8; (2) adding 3.8g of sodium chlorate into the liquid prepared in the step (1) while stirring for oxidation; meanwhile, stirring at a low speed, and when uniform liquid is formed and no bubbles appear, stirring; (3) weighing aluminum sulfate according to the molar ratio of AL/Fe of 1:11, adding distilled water for dissolving, adding the aluminum sulfate into the ferrous sulfate mixed solution in the step (2) after dissolving, and simultaneously stirring uniformly at a slow speed; (4) putting the ferrous sulfate mixed solution into a water bath kettle, and controlling the water bath temperature to be 72 ℃; starting the stirrer, and stirring at a low speed for 40 min; during the polymerization, H was added in a proportion such that the molar ratio P/Fe was 0.253PO4As a stabilizer; (5) stirring for 40min, adding small amount of Na after the liquid is uniform2CO3Adjusting the alkalization degree to 0.3; (6) after stirring, taking out the product, standing for 24 hours to obtain the product, evaporating water and drying to obtain the polymeric aluminum ferric sulfate.
(3) Adsorption separation: adsorbing the extract filtrate with macroporous adsorbent resin, stopping feeding, washing with water, desorbing with 66% ethanol, and collecting desorption solution;
(4) concentration and crystallization: concentrating the desorption solution under reduced pressure to 2.6 times of the feeding amount, adding 95% ethanol, and crystallizing for 10 hours;
(5) centrifugal separation: centrifuging the crystal material by using a centrifugal machine, and leaching by using 95% ethanol to obtain primary crystals;
(6) reverse osmosis concentration: dissolving the primary crystal obtained in the step (5) by using 95% ethanol, and performing reverse osmosis concentration treatment by using a ro membrane; then, desalting and decoloring are carried out: passing the concentrated solution through a cation column and an anion column, desalting and decolorizing, recovering solvent liquid, performing active carbon treatment, and spray drying to obtain a crude product;
(7) and (3) recrystallization: heating and dissolving the crude product and a methanol aqueous solution according to the mass ratio of 1:4-6, keeping the temperature to 18 ℃ after complete dissolution, stirring for 18 minutes every 1.5 hours, and separating the mixture liquid after 40 hours to obtain stevioside crystals;
(8) and (3) post-treatment: dissolving stevioside crystal in water, spray drying to obtain dried stevioside, and pulverizing.
The stevioside prepared in the embodiments 1 to 3 is detected, the total glycoside content is higher than 99 percent, the stevioside A content is higher than 98 percent, and the determination method is carried out according to the stevioside national standard GB8270-2014 of the people's republic of China.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A method for extracting stevioside by a recrystallization method is characterized by comprising the following steps:
(1) raw material extraction: selecting high-quality stevia rebaudiana dry leaves by screening, performing 2-stage countercurrent extraction at the water temperature of 70-90 ℃, and feeding the extract into the next process;
(2) a flocculation procedure: placing the extractive solution in 40-50 deg.C water bath, stirring at constant temperature of 30-60rpm for 10-20min, adding flocculant, adjusting pH to 8-10, standing for 20-50min, and filtering to obtain clarified water extractive solution of stevia rebaudiana Bertoni; the flocculant comprises the following raw materials in parts by weight: 5-9 parts of chitosan, 15-25 parts of lignin, 10-18 parts of ammonium persulfate, 20-25 parts of polyaluminum ferric sulfate, 22-24 parts of aluminum citrate, 2-7 parts of magnesium sulfate, 1-4 parts of calcium chloride, 15-25 parts of polysilicate iron, 3-6 parts of sodium carboxymethylcellulose, 5-7 parts of activated carbon, 1-2 parts of bentonite and 2-4 parts of fly ash;
(3) adsorption separation: adsorbing the filtrate with macroporous adsorbent resin, stopping feeding, washing with water, desorbing with 50-85% ethanol, and collecting desorption solution;
(4) concentration and crystallization: concentrating the desorption solution under reduced pressure to 2-3 times of the feeding amount, adding 95% ethanol, and crystallizing for 5-12 hours;
(5) centrifugal separation: centrifuging the crystal material by using a centrifugal machine, and leaching by using 95% ethanol to obtain primary crystals;
(6) reverse osmosis concentration: dissolving the primary crystal obtained in the step (5) by using 95% ethanol, and performing reverse osmosis concentration treatment by using a ro membrane; then, desalting and decoloring are carried out: passing the concentrated solution through a cation column and an anion column, desalting and decolorizing, recovering solvent liquid, performing active carbon treatment, and spray drying to obtain a crude product;
(7) and (3) recrystallization: heating and dissolving the crude product and a methanol aqueous solution according to the mass ratio of 1:4-6, keeping the temperature to 15-25 ℃ after complete dissolution, stirring for 15-30 minutes every 1-3 hours, and separating the mixture liquid after 36-48 hours to obtain stevioside crystals;
(8) and (3) post-treatment: dissolving stevioside crystal in water, spray drying to obtain dried stevioside, and pulverizing.
2. The method for extracting stevioside according to claim 1, wherein the chitosan in the step (2) is modified chitosan, and the preparation method of the modified chitosan comprises the following steps: soaking chitosan in 95% ethanol for 2-5h, transferring into a reactor, adding vanillin according to the mass ratio of vanillin to chitosan of 2-5: 1-4, stirring and refluxing in water bath with water as a solvent, adding a 10% diluted sodium hydroxide solution, filtering and cleaning, extracting with acetone, removing unreacted vanillin and other impurities, and drying to obtain vanillin modified chitosan.
3. Method for extracting stevioside by recrystallization according to claims 1 to 3The method is characterized in that the preparation of the polymeric aluminum ferric sulfate comprises the following specific steps: (1) putting 50-60g of ferrous sulfate heptahydrate into a beaker, adding distilled water and stirring to form uniform dilute pasty ferrous sulfate mixed solution; then 3-4mL of 98% concentrated H was added slowly with stirring2SO4Acidifying, and adjusting the pH of the mixed solution to 0.6-1.0; (2) adding 3.5-4.3g of sodium chlorate into the liquid prepared in the step (1) while stirring for oxidation; meanwhile, stirring at a low speed, and when uniform liquid is formed and no bubbles appear, stirring; (3) weighing aluminum sulfate according to the molar ratio of AL/Fe of 1: 11-1: 9, adding distilled water for dissolving, adding the aluminum sulfate into the ferrous sulfate mixed solution in the step (2) after dissolving, and simultaneously stirring uniformly at a low speed; (4) putting the ferrous sulfate mixed solution into a water bath kettle, and controlling the water bath temperature to be 60-80 ℃; starting the stirrer, and stirring at a low speed for 30-60 min; in the polymerization reaction process, H is added according to the proportion that the molar ratio of P/Fe is 0.1-0.33PO4As a stabilizer; (5) stirring for 20-45min, adding small amount of Na after the liquid is uniform2CO3Adjusting the alkalization degree to 0.3; (6) and after stirring is finished, taking out the product, standing for 24 hours to obtain the product, evaporating water, and drying to obtain the polymeric aluminum ferric sulfate.
4. A method of extracting steviol glycosides by recrystallization as claimed in claim 1, wherein the flocculation step in step (2): placing the extractive solution in 48 deg.C water bath, stirring at 50rpm for 16min, adding flocculant, adjusting pH to 9, standing for 35min, and filtering to obtain clarified water extractive solution of stevia rebaudiana Bertoni; the flocculant comprises the following raw materials in parts by weight: 5.2-6.3 parts of chitosan, 15.1-18.9 parts of lignin, 11-15.2 parts of ammonium persulfate, 21.3-23.2 parts of polymeric aluminum ferric sulfate, 22.4-23 parts of aluminum citrate, 3.1-5.2 parts of magnesium sulfate, 1.5-2.4 parts of calcium chloride, 16.4-19.5 parts of polysilicate iron, 3.5-4.4 parts of sodium carboxymethyl cellulose, 5.8-6.5 parts of activated carbon, 1.1-1.5 parts of bentonite and 2.3-2.9 parts of fly ash.
5. A method of extracting steviol glycosides according to claim 1, wherein in step (7) the recrystallization: heating the crude product and a methanol aqueous solution according to the mass ratio of 1:5 for dissolving, keeping the temperature to 18 ℃ after complete dissolution, stirring for 20 minutes every 2 hours, and separating the mixture liquid after 40 hours to obtain the stevioside crystal.
6. The method for extracting stevioside according to claim 1, wherein the flocculant comprises the following raw materials in parts by weight: 7.2-8.9 parts of chitosan, 21.2-24.7 parts of lignin, 15.3-17.5 parts of ammonium persulfate, 23.5-24.6 parts of polymeric aluminum ferric sulfate, 23.1-23.5 parts of aluminum citrate, 3.4-6 parts of magnesium sulfate, 3-3.5 parts of calcium chloride, 22-23.8 parts of polysilicate iron, 4.4-5.6 parts of sodium carboxymethyl cellulose, 6.1-6.5 parts of activated carbon, 1.3-1.85 parts of bentonite and 3-3.7 parts of fly ash.
7. The method for extracting stevioside according to claim 1, wherein in step (3), 60% ethanol is further used for desorption, and the desorption solution is collected.
8. The method for extracting stevioside according to claim 1, wherein in the step (4), the stripping solution is concentrated under reduced pressure to 2.2 times of the input amount, and 95% ethanol is added for crystallization for 10 hours.
9. The method for extracting stevioside according to claims 1-8 by recrystallization, wherein the stevioside is extracted by the method, the total glycoside content is higher than 99%, and the stevioside A content is higher than 98%.
10. A steviol glycoside prepared by a process according to claims 1-9.
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| CN111548378A (en) * | 2020-05-21 | 2020-08-18 | 中国药科大学 | Method for purifying stevioside |
| CN114478666A (en) * | 2021-12-31 | 2022-05-13 | 蚌埠市华东生物科技有限公司 | Method for extracting high-purity stevioside from stevia rebaudiana |
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