CN113699196A - Anhydrous enzymatic method catalytic synthesis method of sucrose-6-acetate - Google Patents
Anhydrous enzymatic method catalytic synthesis method of sucrose-6-acetate Download PDFInfo
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- CN113699196A CN113699196A CN202110942046.5A CN202110942046A CN113699196A CN 113699196 A CN113699196 A CN 113699196A CN 202110942046 A CN202110942046 A CN 202110942046A CN 113699196 A CN113699196 A CN 113699196A
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- sucrose
- reaction kettle
- pumping
- molecular sieve
- reaction
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- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000007036 catalytic synthesis reaction Methods 0.000 title description 2
- 238000006911 enzymatic reaction Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000002808 molecular sieve Substances 0.000 claims abstract description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229930006000 Sucrose Natural products 0.000 claims abstract description 19
- 238000005086 pumping Methods 0.000 claims abstract description 19
- 239000005720 sucrose Substances 0.000 claims abstract description 19
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 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 claims abstract description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 8
- 102000004190 Enzymes Human genes 0.000 claims abstract description 7
- 108090000790 Enzymes Proteins 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 102000004882 Lipase Human genes 0.000 claims abstract description 6
- 108090001060 Lipase Proteins 0.000 claims abstract description 6
- 239000004367 Lipase Substances 0.000 claims abstract description 6
- 235000019421 lipase Nutrition 0.000 claims abstract description 6
- 238000004321 preservation Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 235000003599 food sweetener Nutrition 0.000 description 3
- 239000003765 sweetening agent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 235000019640 taste Nutrition 0.000 description 3
- 239000004376 Sucralose Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- BAQAVOSOZGMPRM-QBMZZYIRSA-N sucralose Chemical compound O[C@@H]1[C@@H](O)[C@@H](Cl)[C@@H](CO)O[C@@H]1O[C@@]1(CCl)[C@@H](O)[C@H](O)[C@@H](CCl)O1 BAQAVOSOZGMPRM-QBMZZYIRSA-N 0.000 description 2
- 235000019408 sucralose Nutrition 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 1
- 235000019606 astringent taste Nutrition 0.000 description 1
- 235000019658 bitter taste Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 235000013615 non-nutritive sweetener Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000002905 orthoesters Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000019643 salty taste Nutrition 0.000 description 1
- 235000019614 sour taste Nutrition 0.000 description 1
- 235000019654 spicy taste Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 sucrose ester Chemical class 0.000 description 1
- 125000000185 sucrose group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/12—Disaccharides
Abstract
A method for synthesizing sucrose-6-acetate by anhydrous enzyme catalysis comprises the following steps: drying the molecular sieve for 8-24 h at the drying temperature of 120-300 ℃ by using water; pumping the tertiary amyl alcohol into a reaction kettle, pumping dimethyl sulfoxide into the reaction kettle, and uniformly stirring, wherein the volume ratio of the tertiary amyl alcohol to the dimethyl sulfoxide is 4: 1; adding sucrose into a reaction kettle, starting stirring to completely dissolve the sucrose, pumping vinyl acetate into the reaction kettle, uniformly stirring, controlling the concentration of the sucrose to be 0.03-0.12 mmoL/mL, and controlling the molar ratio of the sucrose to the vinyl acetate to be 1: 5-1: 20; adding molecular sieve at the bottom of the organic resin column, adding lipase into the column, and finally adding the molecular sieve. And (3) carrying out heat preservation reaction at 30 ℃, and pumping the medium in the reaction kettle into the organic resin column at the pump speed of 20 m/L for self-circulation reaction for 8-24 hours. The method has the advantages of simple operation, high efficiency, high conversion rate and low cost.
Description
Technical Field
The invention relates to a method for synthesizing sucrose-6-acetate by catalysis of an anhydrous enzyme method.
Background
Sucralose is a fresh sweetener, which is a novel sweetener developed by the company of England and university of London and applied for patent in 1976, and is the only functional sweetener using sucrose as raw material. The sucralose has the effect of desalting sour and salty tastes, has the effect of covering up unpleasant tastes such as astringent taste, bitter taste, alcoholic taste and the like, has the synergistic effect on the spicy taste and the milk taste, and has a very wide application range. Therefore, the product is the most ideal intense sweetener at present, can be eaten by children, teenagers, adolescents, middle-aged people, old people and patients with various diseases, and has no any nutritional doubt. The method for synthesizing sucrose-6-acetate is mainly a traditional chemical method, such as acetic anhydride esterification, organometallic synthesis, orthoester method, etc., and there are reports about enzymatic synthesis. The chemical synthesis reaction conditions of sucrose ester are generally harsh, the synthesized product has dark color, and by-products are easily generated due to poor selectivity.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for synthesizing sucrose-6-acetate by catalysis in an anhydrous enzyme method, which has the advantages of simple operation, high efficiency, high conversion rate and low cost.
In order to solve the technical problem, the invention provides a method for synthesizing sucrose-6-acetate by catalysis in an anhydrous enzyme method, which comprises the following steps:
(1) pretreatment of a molecular sieve: drying the 4A molecular sieve in a drying oven at the drying temperature of 120-300 ℃ for 8-24 h;
(2) preparing a mixed organic solution: pumping the tertiary amyl alcohol into a reaction kettle, pumping dimethyl sulfoxide into the reaction kettle, and uniformly stirring, wherein the volume ratio of the tertiary amyl alcohol to the dimethyl sulfoxide is 4: 1;
(3) adding sucrose into a reaction kettle, starting stirring to completely dissolve the sucrose, pumping vinyl acetate into the reaction kettle, uniformly stirring, controlling the concentration of the sucrose to be 0.03-0.12 mmoL/mL, and controlling the molar ratio of the sucrose to the vinyl acetate to be 1: 5-1: 20;
(4) adding part of the 4A molecular sieve after high-temperature drying at the bottom of the organic resin column, then putting lipase into the column, and finally adding part of the 4A molecular sieve. And (3) carrying out heat preservation reaction at 30 ℃, and pumping the medium in the reaction kettle into the organic resin column at the pump speed of 20 m/L for self-circulation reaction for 8-24 hours.
The principle and the advantages of the invention are as follows: compared with the prior art, the method has the advantages that lipase can be combined with vinyl acetate into an intermediate compound, can efficiently and specifically act on hydroxyl at the 6 th position of sucrose to perform transesterification, and simultaneously, the molecular sieve and the medium subjected to high-temperature treatment are utilized to fully remove moisture in a reagent machine and a closed space in a reciprocating circulation mode in an organic resin column, so that the balance is effectively moved towards the direction of a product. The method has simple experimental process, avoids the generation of byproducts and the low-efficiency transesterification reaction with poor selectivity. The organic resin column is filled with molecular sieve sucrose-6-acetate, and has the advantages of mild reaction conditions, strong catalytic selectivity, good product safety and the like.
Detailed Description
The first embodiment is as follows:
a method for synthesizing sucrose-6-acetate by anhydrous enzyme catalysis comprises the following steps:
(1) pretreatment of a molecular sieve: drying moisture of 600kg of 4A molecular sieve in a reactor vacuum drying oven at the drying temperature of 300 ℃ for 15 h;
(2) preparing a mixed organic solution: pumping the tert-amyl alcohol obtained by carrying out the high-speed transformation at 4.8m into the reaction kettle, and pumping the dimethyl sulfoxide obtained by carrying out the high-speed transformation at 1.2m into the reaction kettle and uniformly stirring;
(3) adding 123kg (0.06 mol/L) of sucrose into the reaction kettle, starting stirring to completely dissolve the sucrose, pumping 310kg (0.6 mol/L) of vinyl acetate, and uniformly stirring;
(4) after 10m of cultivation, 250kg of the 4A molecular sieve after high-temperature drying is added to the bottom of the organic resin column, 480kg of lipase is then added to the column, and finally 250kg of the 4A molecular sieve is added. And (3) carrying out heat preservation reaction at 30 ℃, and pumping the medium in the reaction kettle into the organic resin column at the pump speed of 20 m/L for self-circulation reaction for 9 hours.
A portion of the supernatant was taken and filtered through a 0.22 um filter into a liquid phase vial. HPLC quantitative analysis was carried out, and the conversion was 97.7% as a result of HPLC.
Example two:
a method for synthesizing sucrose-6-acetate by anhydrous enzyme catalysis comprises the following steps:
(1) pretreatment of a molecular sieve: drying 500kg of 4A molecular sieve in a reactor vacuum drying oven for 24 hours at the drying temperature of 120 ℃;
(2) preparing a mixed organic solution: pumping the tert-amyl alcohol obtained by carrying out the high-speed transformation at 4.8m into the reaction kettle, and pumping the dimethyl sulfoxide obtained by carrying out the high-speed transformation at 1.2m into the reaction kettle and uniformly stirring;
(3) adding 123kg (0.06 mol/L) of sucrose into the reaction kettle, starting stirring to completely dissolve the sucrose, pumping 310kg (0.6 mol/L) of vinyl acetate, and uniformly stirring;
(4) after 10m of cultivation, 250kg of the 4A molecular sieve after high-temperature drying is added to the bottom of the organic resin column, 480kg of lipase is then added to the column, and finally 250kg of the 4A molecular sieve is added. And (3) carrying out heat preservation reaction at 30 ℃, and pumping the medium in the reaction kettle into the organic resin column at the pump speed of 20 m/L for self-circulation reaction for 9 hours.
A portion of the supernatant was taken and filtered through a 0.22 um filter into a liquid phase vial. HPLC quantitative analysis was carried out, and the conversion was 94.1% as a result of HPLC.
Claims (1)
1. A method for synthesizing sucrose-6-acetate by anhydrous enzyme catalysis is characterized by comprising the following steps:
(1) pretreatment of a molecular sieve: drying the 4A molecular sieve in a drying oven at the drying temperature of 120-300 ℃ for 8-24 h;
(2) preparing a mixed organic solution: pumping the tertiary amyl alcohol into a reaction kettle, pumping dimethyl sulfoxide into the reaction kettle, and uniformly stirring, wherein the volume ratio of the tertiary amyl alcohol to the dimethyl sulfoxide is 4: 1;
(3) adding sucrose into a reaction kettle, starting stirring to completely dissolve the sucrose, pumping vinyl acetate into the reaction kettle, uniformly stirring, controlling the concentration of the sucrose to be 0.03-0.12 mmoL/mL, and controlling the molar ratio of the sucrose to the vinyl acetate to be 1: 5-1: 20;
(4) adding the high-temperature dried part of the 4A molecular sieve at the bottom of the organic resin column, then putting lipase into the column, finally adding the part of the 4A molecular sieve, carrying out heat preservation reaction at 30 ℃, and driving the medium in the reaction kettle into the organic resin column at the pump speed of 20m for self-circulation reaction for 8-24 hours.
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| CN202110942046.5A CN113699196A (en) | 2021-08-17 | 2021-08-17 | Anhydrous enzymatic method catalytic synthesis method of sucrose-6-acetate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110942046.5A CN113699196A (en) | 2021-08-17 | 2021-08-17 | Anhydrous enzymatic method catalytic synthesis method of sucrose-6-acetate |
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| CN113699196A true CN113699196A (en) | 2021-11-26 |
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| CN202110942046.5A Pending CN113699196A (en) | 2021-08-17 | 2021-08-17 | Anhydrous enzymatic method catalytic synthesis method of sucrose-6-acetate |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4980463A (en) * | 1989-07-18 | 1990-12-25 | Noramco, Inc. | Sucrose-6-ester chlorination |
| US20080163867A1 (en) * | 2005-02-22 | 2008-07-10 | Molecular Separation Process in Various Steps of Process for Production of Chlorinated Sugars, Their Precursors and Derivatives | |
| CN101759728A (en) * | 2010-01-08 | 2010-06-30 | 江苏巨邦制药有限公司 | Method for preparing and refining sucralose |
| CN101886100A (en) * | 2010-07-12 | 2010-11-17 | 江南大学 | Method for preparing sucrose-6-acetic ester by enzymatic method |
| CN102181494A (en) * | 2011-03-21 | 2011-09-14 | 盐城捷康三氯蔗糖制造有限公司 | Synthesis of sucrose-6-fatty acid ester through selective catalysis of immobilized aspergillus oryzae lipase |
| CN112029754A (en) * | 2020-08-13 | 2020-12-04 | 浙江工业大学 | Imprinted lipase and application thereof in synthesis of sucrose-6-ethyl ester |
-
2021
- 2021-08-17 CN CN202110942046.5A patent/CN113699196A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4980463A (en) * | 1989-07-18 | 1990-12-25 | Noramco, Inc. | Sucrose-6-ester chlorination |
| US20080163867A1 (en) * | 2005-02-22 | 2008-07-10 | Molecular Separation Process in Various Steps of Process for Production of Chlorinated Sugars, Their Precursors and Derivatives | |
| CN101759728A (en) * | 2010-01-08 | 2010-06-30 | 江苏巨邦制药有限公司 | Method for preparing and refining sucralose |
| CN101886100A (en) * | 2010-07-12 | 2010-11-17 | 江南大学 | Method for preparing sucrose-6-acetic ester by enzymatic method |
| CN102181494A (en) * | 2011-03-21 | 2011-09-14 | 盐城捷康三氯蔗糖制造有限公司 | Synthesis of sucrose-6-fatty acid ester through selective catalysis of immobilized aspergillus oryzae lipase |
| CN112029754A (en) * | 2020-08-13 | 2020-12-04 | 浙江工业大学 | Imprinted lipase and application thereof in synthesis of sucrose-6-ethyl ester |
Non-Patent Citations (5)
| Title |
|---|
| 季祥等: "生物质能源及废物利用新技术", 31 December 2012, 吉林大学出版社, pages: 67 - 68 * |
| 李明华;孟秀梅;吴金山;朱国廷;: "离子液体介质中脂肪酶催化合成蔗糖-6-乙酯工艺优化", 中国食品添加剂, no. 11, pages 207 - 48 * |
| 杨绪娥;郑璞;孙志浩;倪晔;: "Lipozyme TL 100L的固定化及其催化合成蔗糖-6-乙酯", 化工进展, no. 11, pages 2517 - 2522 * |
| 王勍等: "非水介质中脂肪酶催化合成蔗糖-6-乙酸酯", 食品与发酵工业, vol. 36, no. 12, pages 4 * |
| 马玲芝;钱俊青;: "离子交换树脂固定化脂肪酶催化合成蔗糖乙酯", 浙江工业大学学报, pages 21 - 24 * |
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