CN114315926B - Technological method for producing steviolbioside by multiple high-temperature pyrolysis - Google Patents
Technological method for producing steviolbioside by multiple high-temperature pyrolysis Download PDFInfo
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- 238000000197 pyrolysis Methods 0.000 title claims abstract description 76
- OMHUCGDTACNQEX-OSHKXICASA-N Steviolbioside Natural products O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@]12C(=C)C[C@@]3(C1)CC[C@@H]1[C@@](C)(CCC[C@]1([C@@H]3CC2)C)C(O)=O)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O OMHUCGDTACNQEX-OSHKXICASA-N 0.000 title claims abstract description 46
- JLPRGBMUVNVSKP-AHUXISJXSA-M chembl2368336 Chemical compound [Na+].O([C@H]1[C@@H](O)[C@H](O)[C@H](CO)O[C@H]1O[C@]12C(=C)C[C@@]3(C1)CC[C@@H]1[C@@](C)(CCC[C@]1([C@@H]3CC2)C)C([O-])=O)[C@@H]1O[C@@H](CO)[C@@H](O)[C@H](O)[C@@H]1O JLPRGBMUVNVSKP-AHUXISJXSA-M 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000012065 filter cake Substances 0.000 claims abstract description 61
- 235000019202 steviosides Nutrition 0.000 claims abstract description 52
- 229940013618 stevioside Drugs 0.000 claims abstract description 50
- OHHNJQXIOPOJSC-UHFFFAOYSA-N stevioside Natural products CC1(CCCC2(C)C3(C)CCC4(CC3(CCC12C)CC4=C)OC5OC(CO)C(O)C(O)C5OC6OC(CO)C(O)C(O)C6O)C(=O)OC7OC(CO)C(O)C(O)C7O OHHNJQXIOPOJSC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000005406 washing Methods 0.000 claims abstract description 49
- UEDUENGHJMELGK-HYDKPPNVSA-N Stevioside Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@]12C(=C)C[C@@]3(C1)CC[C@@H]1[C@@](C)(CCC[C@]1([C@@H]3CC2)C)C(=O)O[C@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O UEDUENGHJMELGK-HYDKPPNVSA-N 0.000 claims abstract description 46
- 238000001914 filtration Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 42
- 238000010438 heat treatment Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 239000008213 purified water Substances 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 238000005336 cracking Methods 0.000 claims abstract description 27
- 239000012043 crude product Substances 0.000 claims abstract description 26
- 238000001816 cooling Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000007670 refining Methods 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- RLLCWNUIHGPAJY-RYBZXKSASA-N Rebaudioside E Natural products O=C(O[C@H]1[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O2)[C@@H](O)[C@@H](O)[C@H](CO)O1)[C@]1(C)[C@@H]2[C@@](C)([C@@H]3[C@@]4(CC(=C)[C@@](O[C@@H]5[C@@H](O[C@@H]6[C@@H](O)[C@H](O)[C@@H](O)[C@H](CO)O6)[C@H](O)[C@@H](O)[C@H](CO)O5)(C4)CC3)CC2)CCC1 RLLCWNUIHGPAJY-RYBZXKSASA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- RLLCWNUIHGPAJY-SFUUMPFESA-N rebaudioside E Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@]12C(=C)C[C@@]3(C1)CC[C@@H]1[C@@](C)(CCC[C@]1([C@@H]3CC2)C)C(=O)O[C@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O[C@H]1[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O1)O)[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O RLLCWNUIHGPAJY-SFUUMPFESA-N 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 6
- -1 stevioside sodium salt Chemical class 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003776 cleavage reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004383 Steviol glycoside Substances 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 235000003599 food sweetener Nutrition 0.000 description 2
- 229930182470 glycoside Natural products 0.000 description 2
- 150000002338 glycosides Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 235000019411 steviol glycoside Nutrition 0.000 description 2
- 229930182488 steviol glycoside Natural products 0.000 description 2
- 150000008144 steviol glycosides Chemical class 0.000 description 2
- 239000003765 sweetening agent Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000228451 Stevia rebaudiana Species 0.000 description 1
- 235000006092 Stevia rebaudiana Nutrition 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
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- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000021096 natural sweeteners Nutrition 0.000 description 1
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Abstract
The invention discloses a process method for producing steviolbioside by a multi-time high-temperature pyrolysis method, which comprises the following steps: (1) Adding 2-15L of purified water into each 1kg of reaction substrate, and fully stirring; (2) Gradually heating the solution to 110-140 ℃ to carry out first pyrolysis for at least 4 hours; (3) cooling to 20-40 ℃ and filtering; (4) Washing the filter cake with purified water at 20-80 ℃ to obtain a stevioside crude product filter cake; (5) Mixing the filtrate and the washing liquid, heating to 120-150 ℃ for secondary cracking for 2-4 hours; (6) cooling the pyrolysis liquid to 20-40 ℃ and filtering; (7) Washing the filter cake with purified water at 20-80 ℃ to obtain a stevioside crude product filter cake; (8) And (3) refining and purifying the crude stevioside filter cake to obtain refined stevioside. The production process of the invention is easier to control, the conversion rate is higher, and the cost of raw materials can be greatly reduced.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation technology of steviolbioside.
Background
Stevioside is a novel natural sweetener extracted from sweet She Juzhong, has the characteristics of high sweetness and low heat energy, is an ideal sweetener capable of replacing sucrose, and is widely applied to industries such as food, beverage, flavoring, brewing, medicine and the like. However, stevioside (STV), the main component of each glycoside of stevioside, has a natural afterbitter or green taste, which also limits its further sugar use.
Steviolbioside (STB) is also one of the sweet components in steviol glycosides. Although the sweetness is weaker than that of stevioside, the afterbitterness is weaker than that of stevioside, so that the taste of steviolbioside is better than that of stevioside. Besides being used as a sweetener, the stevioside compound has the effects of sweetening and reducing blood sugar, and has great application potential. However, the content of steviolbioside in stevioside is very small and less than 1%. If steviolbioside is obtained by means of plant extraction, the steviolbioside is limited by the yield of raw materials and the separation cost, and is difficult to mass produce and popularize.
Because the content of Stevioside (STB) in stevia rebaudiana leaves is low, the existing preparation method is mainly obtained by chemically alkaline hydrolyzing Stevioside (STV) or stevioside (RE) with similar structures, but the chemical hydrolysis method has the disadvantages of extreme reaction conditions, large amount of hazardous waste reagents, high environmental protection pressure and the like.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the defects existing in the prior art, the process method for producing the steviolbioside by a multi-time high-temperature pyrolysis method is easy to control, high in efficiency and rapidness in reaction, high in yield and high in purity.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a process method for producing steviolbioside by a multiple high-temperature pyrolysis method comprises the following steps:
(1) Feeding: adding 2-15L of purified water into each 1kg of reaction substrate, fully stirring, and keeping a stirring state; the reaction substrate is at least one of Stevioside (STV) or Rebaudioside E (RE);
(2) First pyrolysis: gradually heating the solution obtained in the step (1) to 110-140 ℃ to carry out first pyrolysis for at least 4 hours;
(3) And (3) filtering: cooling the pyrolysis liquid after the first pyrolysis to 20-40 ℃, and filtering to obtain filtrate and a filter cake; in order to fully crystallize, the pyrolysis liquid is kept in a stirring state in the cooling process;
(4) Washing: washing the filter cake obtained after filtration by using purified water with the temperature of 20-80 ℃ until the pH value of the eluate is 5-7, and stopping washing to obtain a stevioside crude product filter cake I and a washing liquid;
(5) Second pyrolysis: combining the filtrate obtained in the step (3) and the washing liquid obtained in the step (4), and heating to 120-150 ℃ to carry out secondary pyrolysis for 2-4 hours;
(6) And (3) filtering: cooling the cracking liquid after the second cracking to 20-40 ℃ and filtering; in order to fully crystallize, the pyrolysis liquid is kept in a stirring state in the cooling process;
(7) Washing: washing the filter cake obtained after filtration by using purified water with the temperature of 20-80 ℃ until the pH value of the eluate is 5-7, and stopping washing to obtain a stevioside crude product filter cake II;
(8) Refining: and mixing and dissolving the stevioside crude product filter cake I and the stevioside crude product filter cake II, and further refining and purifying to obtain a stevioside refined product.
As a preferable technical scheme, the cracking temperature in the first high-temperature cracking is 120-130 ℃; the cracking time is 5-9 hours.
As an improved technical scheme, the method of gradually heating the solution in the first high-temperature pyrolysis and the method of gradient heating are adopted in the pyrolysis, and after the temperature of the pyrolysis solution is raised to be more than 100 ℃, the method of gradient heating pyrolysis is adopted, wherein the temperature is kept for 0.5-2.5 hours at 5-10 ℃ per rise.
As a further improved technical scheme, the solution is gradually heated during the first high-temperature pyrolysis and the temperature of the pyrolysis is gradually raised by a gradient temperature raising method, and after the temperature of the pyrolysis solution is raised to be more than 100 ℃, the pyrolysis method with the gradient temperature raising is adopted, wherein the temperature is kept for 1 hour at every 5 ℃.
As an improved technical scheme, the pressure is controlled to be 0.2-3 MPa during the first high-temperature pyrolysis and the second high-temperature pyrolysis.
As an improved technical scheme, the refining step comprises the following steps: adding the filter cake into 5-15 times of 10-40% ethanol based on the stevioside crude product filter cake, heating to 60-85 ℃, preserving heat, slowly adding 35-45 wt% NaOH solution (100 ml purified water is used for dissolving 35-45 g NaOH solid) until the filter cake is fully dissolved, preserving heat and stirring for 5-20 min, slowly adding 35-45 wt% citric acid solution (100 ml purified water is used for dissolving 35-45 g citric acid solid) until the pH value of the solution is 4-5.5, continuously and uniformly stirring for more than 1h in a heat preservation state, filtering, washing the obtained filter cake with 2-5 times of 50-80 ℃ purified water until the pH value of an eluate is 5-7, and drying to obtain a stevioside refined product.
As a preferable technical scheme, the filter cake is added into 10-15 times of 20% ethanol by taking the stevioside crude product filter cake as a reference, and the filter cake is heated to 65-70 ℃ and then is insulated.
As a preferable technical scheme, the filter cake obtained after filtration is washed by 2-5 times of purified water with the temperature of 65-75 ℃ until the pH value of the eluate is 5-7, and then the extract of stevioside is obtained after drying.
The structural general formula of steviol glycoside is shown in the following table 1.
TABLE 1
As an improved technical scheme, the refined stevioside is added with alkali to prepare the sodium salt of the stevioside.
As a further improved technical scheme, the dry weight of the refined stevioside is used: purified water = 1:0.5 to 1:5, adding purified water in proportion, stirring into slurry, adding 35-45 wt% NaOH solution (100 ml of purified water is dissolved into 35-45 g of NaOH solid) to adjust the pH to 7-8.5, heating to dissolve, filtering, and spray drying the filtered clear solution to obtain stevioside sodium salt.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
at least one of Stevioside (STV) or Rebaudioside E (RE) is adopted as a reaction substrate, and is dissolved in purified water only, and stevioside double glycoside is prepared through two high-temperature cracking, and the cracking condition is mild, so that the product which is cracked in the earlier stage is not damaged, and the raw materials which are not cracked can be further and fully cracked in the second cracking; the production process is green and environment-friendly, no other harmful substances are discharged, and the older process is pollution-free.
The product obtained by the twice high-temperature cracking production process has higher purity, and related impurities and bacteria reach the standards; the product yield of the invention can reach more than 75.2 percent, and the product purity can reach more than 97.0 percent.
The invention adopts a gradient heating method when the temperature of the solution is gradually increased and the solution is cracked in the first high-temperature cracking, and adopts a gradient heating cracking method of keeping the temperature for 0.5 to 2.5 hours at 5 to 10 ℃ when the temperature of the solution is increased to be more than 100 ℃. And the cracking is carried out for a period of time at each gradient temperature, so that the generation of byproducts is effectively reduced, and the damage to the cracked products is avoided, and the reaction conversion rate and the product purity are greatly improved.
The invention uses ethanol to dissolve during refining, improves single-step yield, and finally improves product content.
The invention further prepares the STB essence into sodium salt, thereby improving the solubility of STB.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Example 1
(1) Feeding: adding 5L of purified water according to each 1kg of reaction substrate STV, and maintaining a stirring state after fully stirring;
(2) First pyrolysis: controlling the pressure to be 1MPa, gradually heating the solution obtained in the step (1) to 115 ℃ for first pyrolysis, and carrying out pyrolysis for 8 hours;
(3) And (3) filtering: cooling the pyrolysis liquid after the first pyrolysis to 25 ℃, and filtering to obtain filtrate and a filter cake; in order to fully crystallize, the pyrolysis liquid is kept in a stirring state in the cooling process;
(4) Washing: washing the filter cake obtained after filtration by using purified water with the temperature of 60 ℃ until the pH value of an eluate is 6, and stopping washing to obtain a STB crude product filter cake I and a washing liquid;
(5) Second pyrolysis: controlling the pressure to be 1MPa, combining the filtrate in the step (3) and the washing liquid in the step (4), and heating to 125 ℃ for secondary cracking for 4 hours;
(6) And (3) filtering: cooling the cracking liquid after the second cracking to 25 ℃ and filtering; in order to fully crystallize, the pyrolysis liquid is kept in a stirring state in the cooling process;
(7) Washing: washing the filter cake obtained after filtration by using purified water with the temperature of 60 ℃ until the pH value of an eluate is 6, and stopping washing to obtain a STB crude product filter cake II;
(8) Refining: mixing the STB crude product filter cake I and the STB crude product filter cake II, adding the mixture into 6 times of 20% ethanol, heating to 80 ℃, preserving heat, slowly adding 38wt% NaOH solution until the filter cake is fully dissolved, preserving heat and stirring for 10min, then slowly adding 38wt% citric acid solution until the pH value of the solution is 5.0, continuously and uniformly stirring for 1.5h in a heat preservation state, washing the filter cake obtained after filtering with 3 times of 60 ℃ purified water until the pH value of an eluate is 6, and drying to obtain STB fine products. The purity of the product is 97.1 percent and the yield is 75.2 percent.
Example 2
(1) Feeding: adding 10L of purified water into each 1kg of reaction substrate RE, and keeping a stirring state after fully stirring;
(2) First pyrolysis: controlling the pressure to be 2MPa, heating the solution in the step (1) to 100 ℃ by adopting a gradient heating method, and gradually heating to 120 ℃ for first pyrolysis by adopting a gradient heating pyrolysis method of keeping the temperature at 10 ℃ for 2 hours when the temperature of the pyrolysis solution is raised to 100 ℃;
(3) And (3) filtering: cooling the pyrolysis liquid after the first pyrolysis to 30 ℃, and filtering to obtain filtrate and a filter cake; in order to fully crystallize, the pyrolysis liquid is kept in a stirring state in the cooling process;
(4) Washing: washing the filter cake obtained after filtration by using purified water with the temperature of 70 ℃ until the pH value of an eluate is 6.5, and stopping washing to obtain a STB crude product filter cake I and a washing liquid;
(5) Second pyrolysis: controlling the pressure to be 1MPa, combining the filtrate in the step (3) and the washing liquid in the step (4), and heating to 130 ℃ for secondary cracking for 3 hours;
(6) And (3) filtering: cooling the cracking liquid after the second cracking to 30 ℃ and filtering; in order to fully crystallize, the pyrolysis liquid is kept in a stirring state in the cooling process;
(7) Washing: washing the filter cake obtained after filtration by using purified water with the temperature of 70 ℃ until the pH value of an eluate is 6.5, and stopping washing to obtain a STB crude product filter cake II;
(8) Refining: mixing the STB crude product filter cake I and the STB crude product filter cake II, adding the mixture into 10 times of 30% ethanol, heating to 75 ℃, preserving heat, slowly adding 40wt% NaOH solution until the filter cake is fully dissolved, preserving heat and stirring for 15min, then slowly adding 40wt% citric acid solution until the pH value of the solution is 4.5, continuously and uniformly stirring for 1h in a heat preservation state, filtering, washing the filter cake obtained after filtering by using 4 times of 70 ℃ purified water until the pH value of an eluate is 5.5, and drying to obtain the STB fine product. The purity of the product was 97.9% and the yield was 76.2%.
Example 3
(1) Feeding: adding 11L of purified water according to each 1kg of reaction substrate STV, and maintaining a stirring state after fully stirring;
(2) First pyrolysis: controlling the pressure to be 1.8MPa, heating the solution in the step (1) to 105 ℃ by adopting a gradient heating method, and gradually heating to 130 ℃ to perform first pyrolysis by adopting a gradient heating pyrolysis method of keeping the temperature at 5 ℃ for 1.0 hour when the temperature of the pyrolysis solution is raised to 105 ℃ for 5 hours;
(3) And (3) filtering: cooling the pyrolysis liquid after the first pyrolysis to 35 ℃, and filtering to obtain filtrate and a filter cake; in order to fully crystallize, the pyrolysis liquid is kept in a stirring state in the cooling process;
(4) Washing: washing the filter cake obtained after filtration by using purified water with the temperature of 72 ℃ until the pH value of an eluate is 7, and stopping washing to obtain a STB crude product filter cake I and a washing liquid;
(5) Second pyrolysis: controlling the pressure to be 1MPa, combining the filtrate in the step (3) and the washing liquid in the step (4), and heating to 135 ℃ for secondary cracking for 3.5 hours;
(6) And (3) filtering: cooling the cracking liquid after the second cracking to 35 ℃ and filtering; in order to fully crystallize, the pyrolysis liquid is kept in a stirring state in the cooling process;
(7) Washing: washing the filter cake obtained after filtration by using purified water with the temperature of 72 ℃ until the pH value of an eluate is 7, and stopping washing to obtain a STB crude product filter cake II;
(8) Refining: mixing the STB crude product filter cake I and the STB crude product filter cake II, adding the mixture into 12 times of 25% ethanol, heating to 82 ℃, preserving heat, slowly adding 42wt% NaOH solution until the filter cake is fully dissolved, preserving heat and stirring for 8min, then slowly adding 42wt% citric acid solution until the pH value of the solution is 4, continuously and uniformly stirring for 1.2h in a heat preservation state, washing the filter cake obtained after filtering by 3 times of 75 ℃ purified water until the pH value of an eluate is 7, and drying to obtain an STB fine product. The purity of the product is 97.8 percent and the yield is 76.8 percent.
Example 4
STB essence prepared in examples 1, 2 and 3 were used, and dry weight of STB essence was used: purified water = 1:1.1 adding purified water in proportion, stirring into slurry, adding 35wt% NaOH solution to adjust pH to 7.5, heating to dissolve, filtering, and spray drying the filtered clear solution to obtain STB sodium salt.
Comparative test example 1
Comparative test example 1 the process of example 1 was used, except that the temperature and time of the two lyses were different. The yields of the corresponding crude STB under different cleavage conditions are shown in table 2.
TABLE 2
As can be seen from table 2:
the higher the temperature, the higher the conversion at 5 hours of first cleavage and 2 hours of second cleavage; the cracking time is prolonged, and the conversion rate is firstly improved and then reduced along with the temperature increase and is in a parabolic form. The STB conversion rate is only 31.1% after 9 hours of first 130+ -5deg.C cracking and 4 hours of second 140+ -5deg.C cracking; it shows that under the high temperature condition, the heat preservation time is too long, and the converted STB is partially destroyed.
Comparative test example 2
Comparative test example 2 differs from example 1 in that: the STB refined product obtained by refining after dissolution with the same amount of water has a purity of 94.3% and a yield of 75.1%.
Comparative test example 3
Comparative test example 3 differs from example 3 in that: the first pyrolysis does not adopt a gradient heating method, and the temperature of the pyrolysis liquid is gradually increased to 130 ℃ to carry out the first pyrolysis for 5 hours. The purity of the obtained STB refined product is 95.1% and the yield is 71.4%.
Claims (7)
1. A process method for producing steviolbioside by a multiple high-temperature pyrolysis method is characterized by comprising the following steps:
(1) Feeding: adding 2-15L of purified water into each 1kg of reaction substrate, fully stirring, and keeping a stirring state; the reaction substrate is at least one of stevioside or rebaudioside E;
(2) First pyrolysis: gradually heating the solution obtained in the step (1) to 120-130 ℃ to carry out first pyrolysis, wherein the pyrolysis time is 5-9 hours; the method of gradually heating the dissolution liquid in the first high-temperature pyrolysis and adopting a gradient heating method in the pyrolysis, wherein after the temperature of the pyrolysis liquid is raised to be more than 100 ℃, the method of gradient heating pyrolysis which is carried out for 0.5-2.5 hours at the temperature of 5-10 ℃ in each rise is adopted;
(3) And (3) filtering: cooling the pyrolysis liquid after the first pyrolysis to 20-40 ℃, and filtering to obtain filtrate and a filter cake; in order to fully crystallize, the pyrolysis liquid is kept in a stirring state in the cooling process;
(4) Washing: washing the filter cake obtained after filtration by using purified water with the temperature of 20-80 ℃ until the pH value of the eluate is 5-7, and stopping washing to obtain a stevioside crude product filter cake I and a washing liquid;
(5) Second pyrolysis: combining the filtrate obtained in the step (3) and the washing liquid obtained in the step (4), and heating to 125-135 ℃ for secondary pyrolysis for 3-4 hours;
(6) And (3) filtering: cooling the cracking liquid after the second cracking to 20-40 ℃ and filtering; in order to fully crystallize, the pyrolysis liquid is kept in a stirring state in the cooling process;
(7) Washing: washing the filter cake obtained after filtration by using purified water with the temperature of 20-80 ℃ until the pH value of the eluate is 5-7, and stopping washing to obtain a stevioside crude product filter cake II;
(8) Refining: and mixing and dissolving the stevioside crude product filter cake I and the stevioside crude product filter cake II, and further refining and purifying to obtain a stevioside refined product.
2. The process for producing steviolbioside by multiple pyrolysis according to claim 1, wherein: the pressure is controlled to be 0.2-3 MPa during the first high-temperature pyrolysis and the second high-temperature pyrolysis.
3. The process for producing steviolbioside by multiple pyrolysis according to claim 1, wherein the refining step comprises: adding the filter cake into 5-15 times of 10-40% ethanol based on the stevioside crude product filter cake, heating to 60-85 ℃, preserving heat, slowly adding 35-45 wt% NaOH solution until the filter cake is fully dissolved, preserving heat, stirring for 5-20 min, slowly adding 35-45 wt% citric acid solution until the pH value of the solution is 4-5.5, continuously and uniformly stirring for more than 1h in a heat preservation state, filtering, washing the filter cake obtained after filtering by using 2-5 times of 50-80 ℃ purified water until the pH value of an eluate is 5-7, and drying to obtain the stevioside refined product.
4. A process for producing steviolbioside by multiple pyrolysis according to claim 3, wherein: taking the stevioside crude product filter cake as a reference, putting the filter cake into 10-15 times of 20% ethanol, heating to 65-70 ℃ and then preserving heat.
5. A process for producing steviolbioside by multiple pyrolysis according to claim 3, wherein: and (3) washing the filter cake obtained after filtering with 2-5 times of purified water at 65-75 ℃ until the pH value of the eluate is 5-7, and drying to obtain refined stevioside.
6. The process for producing steviolbioside by multiple pyrolysis according to claim 1, wherein: adding alkali into the refined stevioside to prepare the stevioside sodium salt.
7. The process for producing steviolbioside by multiple pyrolysis according to claim 6, wherein: dry weight of steviolbioside fine product: purified water = 1:0.5 to 1:5 adding purified water in proportion, stirring into slurry, adding 35-45 wt% NaOH solution to adjust pH to 7-8.5, heating to dissolve, filtering, and spray drying the filtered clear solution to obtain stevioside sodium salt.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4404367A (en) * | 1981-08-26 | 1983-09-13 | Dynapol | Glucosubstituented diterpenoid sweeteners |
| US4454290A (en) * | 1980-09-22 | 1984-06-12 | Dynapol | Stevioside analogs |
| CN104151378A (en) * | 2014-08-12 | 2014-11-19 | 济南汉定生物工程有限公司 | Rebaudioside M purification method |
| CN112513059A (en) * | 2018-03-16 | 2021-03-16 | 谱赛科美国股份有限公司 | High purity steviol glycosides |
| CN113583064A (en) * | 2021-08-28 | 2021-11-02 | 诸城市浩天药业有限公司 | Process method for producing rebaudioside B by high-temperature cracking method |
-
2022
- 2022-01-04 CN CN202210004860.7A patent/CN114315926B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4454290A (en) * | 1980-09-22 | 1984-06-12 | Dynapol | Stevioside analogs |
| US4404367A (en) * | 1981-08-26 | 1983-09-13 | Dynapol | Glucosubstituented diterpenoid sweeteners |
| CN104151378A (en) * | 2014-08-12 | 2014-11-19 | 济南汉定生物工程有限公司 | Rebaudioside M purification method |
| CN112513059A (en) * | 2018-03-16 | 2021-03-16 | 谱赛科美国股份有限公司 | High purity steviol glycosides |
| CN113583064A (en) * | 2021-08-28 | 2021-11-02 | 诸城市浩天药业有限公司 | Process method for producing rebaudioside B by high-temperature cracking method |
Non-Patent Citations (1)
| Title |
|---|
| Thermal characterization and compounds identification of commercial Stevia rebaudiana Bertoni sweeteners and thermal degradation products at high temperatures by TG–DSC, IR and LC–MS/MS;Gonçalves Nunes;《Journal of Thermal Analysis and Calorimetry 》;第146卷(第3期);1149–1155 * |
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