阅读说明：本技术 一种蔗糖-6-乙酸酯的无水酶法催化合成方法 (Anhydrous enzymatic method catalytic synthesis method of sucrose-6-acetate ) 是由 祁飞 戴永辉 朱岁繁 于 2021-08-17 设计创作，主要内容包括：一种蔗糖-6-乙酸酯的无水酶法催化合成方法,包括以下步骤：将分子筛烘干水分,烘干温度为120～300℃,烘干时间为8～24h；将叔戊醇泵入反应釜中,再泵入二甲基亚砜搅拌均匀,其中叔戊醇与二甲基亚砜的体积比为4:1；向反应釜内投入蔗糖,然后开启搅拌使其完全溶解,再泵入乙酸乙烯酯,搅拌均匀,控制蔗糖浓度为0.03～0.12mmoL/mL,蔗糖与乙酸乙烯酯的摩尔比为1:5～1:20；在有机树脂柱底部加分子筛,随后投入脂肪酶于柱子中,最后再加分子筛。30℃保温反应,把反应釜中的介质以20m??/L的泵速打到有机树脂柱中自循环反应8～24h即可。该方法操作简单、效率高、转化率高且成本低。(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.)

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.

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.