CN111548375A - Improved sucralose chlorination liquid post-treatment method - Google Patents
Improved sucralose chlorination liquid post-treatment method Download PDFInfo
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- CN111548375A CN111548375A CN202010439212.5A CN202010439212A CN111548375A CN 111548375 A CN111548375 A CN 111548375A CN 202010439212 A CN202010439212 A CN 202010439212A CN 111548375 A CN111548375 A CN 111548375A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
- C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
- C07H13/04—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals attached to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H5/00—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium
- C07H5/02—Compounds containing saccharide radicals in which the hetero bonds to oxygen have been replaced by the same number of hetero bonds to halogen, nitrogen, sulfur, selenium, or tellurium to halogen
Abstract
The invention discloses an improved sucralose chlorination liquid post-treatment method, which comprises the following steps: I) adding weak base into sucralose chlorination liquid for quenching, and obtaining suspension after quenching; the temperature during quenching is 0-10 ℃, and the pH value during quenching is adjusted to 9.5-11.0; II) directly adding acid into the suspension for neutralization until the pH value is 6.5-7.5, and filtering after neutralization to obtain filter residue and filtrate containing sucralose-6-acetate. The treatment method can solve the technical difficulties of difficult treatment and filtration, low yield, unstable yield and the like after chlorination reaction in the production process of sucralose.
Description
Technical Field
The invention belongs to the field of sucralose synthesis, and particularly relates to a method for post-treatment of sucralose chlorination liquid, which can solve the technical difficulties of low post-treatment yield, unstable yield and the like in the production process of sucralose.
Background
The demand of high-grade food additives is increasing day by day, and sucralose is the most ideal high sweetener among the sweeteners, and the research on the high sweetener sucralose conforms to the development demand. At present, a plurality of domestic sucralose manufacturers produce sucralose, and the sucralose chlorination process is mostly synthesized by using vilsmiier reagent.
The sucralose chlorination process is a reaction with high selectivity, and the preparation of the vilsmiier reagent by using thionyl chloride is simple and safe to operate, but has poor chlorination effect, long period, low conversion rate and complex subsequent treatment. The prior art discloses that the pH value is generally 9.0-9.5 when inorganic alkali sodium hydroxide, potassium hydroxide and ammonia water are used for chlorination quenching, but the influence of the pH in the chlorination post-treatment process on the reaction is lack of relevant research, so that the reaction yield is greatly influenced, and the wastewater amount and the production cost are related.
Disclosure of Invention
The technical problem to be solved by the invention is to provide an improved method for post-treating sucralose chlorination liquid, and when the method is used for treating the sucralose chlorination liquid, the reaction yield can be effectively improved by selecting proper pH.
The technical scheme of the sampling point of the invention is as follows:
an improved sucralose chlorination liquid post-treatment method comprises the following steps:
I) adding weak base into sucralose chlorination liquid for quenching, and obtaining suspension after quenching; the temperature during quenching is 0-10 ℃, and the pH value during quenching is adjusted to 9.5-11.0;
II) directly adding acid into the suspension for neutralization until the pH value is 6.5-7.5, and filtering after neutralization to obtain filter residue and filtrate containing sucralose-6-acetate.
The further technical scheme is that the weak base is ammonia water, the pH value is adjusted to 9.5-11.0 during quenching, and the reaction is kept for half an hour.
The further technical scheme is that the pH value is preferably 10.0-10.5 during quenching.
The further technical scheme is that acid used for neutralization is hydrochloric acid, and the pH value is preferably 7.0-7.5 during neutralization.
When sucrose is used as a starting material to synthesize sucralose, reaction steps such as esterification, acylation, chlorination, deacylation and the like are required, and the sucralose chlorination solution of the invention refers to a two-phase sucralose-6-acetate-containing solution obtained after the chlorination step is finished. The chlorination step is carried out using Vilsmeier reagent (thionyl chloride/DMF).
After the chlorination stage is finished, the chlorination liquid is adjusted to be in a proper pH value by adopting ammonia water, is adjusted to be neutral by using acid, and achieves the purposes of simplifying post-treatment procedures and improving yield after filtering and desalting, and the filtrate enters the next procedure.
And concentrating, deacylating, extracting, crystallizing and drying the treated chlorinated solution to obtain the finished product of sucralose. Wherein, the steps of concentration, deacylation, extraction, crystallization, drying and the like can be carried out according to the technical scheme reported in the prior art.
The filtration mode can be vacuum filtration, filter pressing or centrifugal filtration, and the obtained filter residue is generated salt plus flocculated carbide and caramel impurities.
Compared with the prior art, the invention has the beneficial effects that:
(1) after quenching, neutralizing and filtering, so that the working procedure and the cost are saved;
(2) can improve the yield of the sucralose-6-acetate by more than 10 percent.
Detailed Description
Example 1
Preparation of sucralose-6-acetate
127 mL of trichloroethane was added to a 500mL three-necked flask, and the mixture was stirred and cooled to a temperature of 0 ℃ or lower. And (3) dropwise adding 29 mL of thionyl chloride into the reaction bottle by using a constant-pressure titration funnel, wherein the temperature is not more than 5 ℃, uniformly stirring, and stirring for 20 min after the dropwise adding is finished. And (3) dropwise adding 50ml of DMF solution of sucrose-6-acetate with the concentration content of sucrose-6-acetate of 340g/L into the mixed solution by using a dropping funnel, uniformly stirring at the temperature of not more than 10 ℃, naturally returning to the room temperature after dropwise adding, and stirring for 30 min at the room temperature.
Heating and stirring the mixture in an oil bath kettle to 68-71 ℃, adopting gradient heating to ensure that the heating time is more than 1h, and keeping the temperature for 50 min after the temperature is reached. And (4) performing gradient temperature rise, wherein the temperature rise is carried out to 90 ℃, the temperature rise time is more than 1h, and the temperature is kept for 30 min after the temperature is reached. Heating to 98-101 deg.c for 1 hr and maintaining for 1.5 hr. The temperature is increased to 109-112 ℃, the temperature rise time is more than 1h, and the temperature is kept for 2 h after the temperature is reached. And after the reaction is finished, naturally cooling to room temperature.
Cooling to below 0 deg.C, adding dropwise ammonia water into the mixture with dropping funnel until the pH of the mixture is 8.5 (the temperature is not more than 10 deg.C). Hydrochloric acid was then added dropwise to the mixture using a dropping funnel until the pH of the mixture was 7.0. And (4) carrying out suction filtration under reduced pressure, sampling from the mixed solution, and carrying out HPLC detection, wherein the yield of the sucralose-6-acetate is 36%.
Example 2
127 mL of trichloroethane was added to a 500mL three-necked flask, and the mixture was stirred and cooled to a temperature of 0 ℃ or lower. And (3) dropwise adding 29 mL of thionyl chloride into the reaction bottle by using a constant-pressure titration funnel, wherein the temperature is not more than 5 ℃, uniformly stirring, and stirring for 20 min after the dropwise adding is finished. And dropwise adding 50mL of DMF (340 g/L concentration) solution of sucrose-6-acetate into the mixed solution by using a dropping funnel, keeping the temperature below 10 ℃, uniformly stirring, naturally returning to the room temperature after dropwise adding, and stirring for 30 min at the room temperature.
Heating and stirring the mixture in an oil bath kettle to 68-71 ℃, adopting gradient heating to ensure that the heating time is more than 1h, and keeping the temperature for 50 min after the temperature is reached. And (4) performing gradient temperature rise, wherein the temperature rise is carried out to 90 ℃, the temperature rise time is more than 1h, and the temperature is kept for 30 min after the temperature is reached. Heating to 98-101 deg.c for 1 hr and maintaining for 1.5 hr. The temperature is increased to 109-112 ℃, the temperature rise time is more than 1h, and the temperature is kept for 2 h after the temperature is reached. And after the reaction is finished, naturally cooling to room temperature.
Cooling to below 0 deg.C, adding dropwise ammonia water into the mixture with dropping funnel until the pH of the mixture is 9 (the temperature is not more than 10 deg.C). Hydrochloric acid was then added dropwise to the mixture using a dropping funnel until the pH of the mixture was 7.0. And (4) carrying out suction filtration under reduced pressure, sampling from the mixed solution, and carrying out HPLC detection, wherein the yield of the sucralose-6-acetate is 50%.
Example 3
127 mL of trichloroethane was added to a 500mL three-necked flask, and the mixture was stirred and cooled to a temperature of 0 ℃ or lower. And (3) dropwise adding 29 mL of thionyl chloride into the reaction bottle by using a constant-pressure titration funnel, wherein the temperature is not more than 5 ℃, uniformly stirring, and stirring for 20 min after the dropwise adding is finished. And dropwise adding 50mL of DMF (340 g/L) solution of sucrose-6-acetate into the mixed solution by using a dropping funnel, keeping the temperature below 10 ℃, uniformly stirring, naturally returning to the room temperature after dropwise adding, and stirring for 30 min at the room temperature. Heating and stirring the mixture in an oil bath kettle to 68-71 ℃, adopting gradient heating to ensure that the heating time is more than 1h, and keeping the temperature for 50 min after the temperature is reached. And (4) performing gradient temperature rise, wherein the temperature rise is carried out to 90 ℃, the temperature rise time is more than 1h, and the temperature is kept for 30 min after the temperature is reached. Heating to 98-101 deg.c for 1 hr and maintaining for 1.5 hr. The temperature is increased to 109-112 ℃, the temperature rise time is more than 1h, and the temperature is kept for 2 h after the temperature is reached. And after the reaction is finished, naturally cooling to room temperature.
Cooling to below 0 deg.C, adding ammonia water dropwise into the mixture with dropping funnel until the pH of the mixture is 9.5, and maintaining the pH for half an hour (the temperature is not more than 10 deg.C). Hydrochloric acid was then added dropwise to the mixture using a dropping funnel until the pH of the mixture was 7.0. And (4) carrying out suction filtration under reduced pressure, sampling from the mixed solution, and carrying out HPLC detection to obtain the sucralose-6-acetate yield of 63%.
Example 4
127 mL of trichloroethane was added to a 500mL three-necked flask, and the mixture was stirred and cooled to a temperature of 0 ℃ or lower. And (3) dropwise adding 29 mL of thionyl chloride into the reaction bottle by using a constant-pressure titration funnel, wherein the temperature is not more than 5 ℃, uniformly stirring, and stirring for 20 min after the dropwise adding is finished. And dropwise adding 50mL of DMF (340 g/L) solution of sucrose-6-acetate into the mixed solution by using a dropping funnel, keeping the temperature below 10 ℃, uniformly stirring, naturally returning to the room temperature after dropwise adding, and stirring for 30 min at the room temperature. Heating and stirring the mixture in an oil bath kettle to 68-71 ℃, adopting gradient heating to ensure that the heating time is more than 1h, and keeping the temperature for 50 min after the temperature is reached. And (4) performing gradient temperature rise, wherein the temperature rise is carried out to 90 ℃, the temperature rise time is more than 1h, and the temperature is kept for 30 min after the temperature is reached. Heating to 98-101 deg.c for 1 hr and maintaining for 1.5 hr. The temperature is increased to 109-112 ℃, the temperature rise time is more than 1h, and the temperature is kept for 2 h after the temperature is reached. And after the reaction is finished, naturally cooling to room temperature.
Cooling to below 0 deg.C, adding ammonia water dropwise into the mixture with dropping funnel until the pH of the mixture is 10.0, and maintaining the pH for half an hour (the temperature is not more than 10 deg.C). Hydrochloric acid was then added dropwise to the mixture using a dropping funnel until the pH of the mixture was 7.0. And (4) carrying out suction filtration under reduced pressure, sampling from the mixed solution, and carrying out HPLC detection, wherein the yield of the sucralose-6-acetate is 73%.
Example 5
127 mL of trichloroethane was added to a 500mL three-necked flask, and the mixture was stirred and cooled to a temperature of 0 ℃ or lower. And (3) dropwise adding 29 mL of thionyl chloride into the reaction bottle by using a constant-pressure titration funnel, wherein the temperature is not more than 5 ℃, uniformly stirring, and stirring for 20 min after the dropwise adding is finished. And dropwise adding 50mL of DMF (340 g/L) solution of sucrose-6-acetate into the mixed solution by using a dropping funnel, keeping the temperature below 10 ℃, uniformly stirring, naturally returning to the room temperature after dropwise adding, and stirring for 30 min at the room temperature. Heating and stirring the mixture in an oil bath kettle to 68-71 ℃, adopting gradient heating to ensure that the heating time is more than 1h, and keeping the temperature for 50 min after the temperature is reached. And (4) performing gradient temperature rise, wherein the temperature rise is carried out to 90 ℃, the temperature rise time is more than 1h, and the temperature is kept for 30 min after the temperature is reached. Heating to 98-101 deg.c for 1 hr and maintaining for 1.5 hr. The temperature is increased to 109-112 ℃, the temperature rise time is more than 1h, and the temperature is kept for 2 h after the temperature is reached. And after the reaction is finished, naturally cooling to room temperature.
Cooling to below 0 deg.C, adding ammonia water dropwise into the mixture with dropping funnel until the pH of the mixture is 10.5, and maintaining the pH for half an hour (the temperature is not more than 10 deg.C). Hydrochloric acid was then added dropwise to the mixture using a dropping funnel until the pH of the mixture was 7.0. And (4) carrying out suction filtration under reduced pressure, sampling from the mixed solution, and carrying out HPLC detection, wherein the yield of the sucralose-6-acetate is 77%.
Example 6
127 mL of trichloroethane was added to a 500mL three-necked flask, and the mixture was stirred and cooled to a temperature of 0 ℃ or lower. And (3) dropwise adding 29 mL of thionyl chloride into the reaction bottle by using a constant-pressure titration funnel, wherein the temperature is not more than 5 ℃, uniformly stirring, and stirring for 20 min after the dropwise adding is finished. And dropwise adding 50mL of DMF (340 g/L) solution of sucrose-6-acetate into the mixed solution by using a dropping funnel, keeping the temperature below 10 ℃, uniformly stirring, naturally returning to the room temperature after dropwise adding, and stirring for 30 min at the room temperature. Heating and stirring the mixture in an oil bath kettle to 68-71 ℃, adopting gradient heating to ensure that the heating time is more than 1h, and keeping the temperature for 50 min after the temperature is reached. And (4) performing gradient temperature rise, wherein the temperature rise is carried out to 90 ℃, the temperature rise time is more than 1h, and the temperature is kept for 30 min after the temperature is reached. Heating to 98-101 deg.c for 1 hr and maintaining for 1.5 hr. The temperature is increased to 109-112 ℃, the temperature rise time is more than 1h, and the temperature is kept for 2 h after the temperature is reached. And after the reaction is finished, naturally cooling to room temperature.
Cooling to below 0 deg.C, adding ammonia water dropwise into the mixture with dropping funnel until the pH of the mixture is 11.0 (the temperature is not more than 10 deg.C). Hydrochloric acid was then added dropwise to the mixture using a dropping funnel until the pH of the mixture was 7.0. And (4) carrying out suction filtration under reduced pressure, sampling from the mixed solution, and carrying out HPLC detection, wherein the yield of the sucralose-6-acetate is 65%.
Claims (4)
1. An improved sucralose chlorination liquid post-treatment method is characterized by comprising the following steps:
I) adding weak base into sucralose chlorination liquid for quenching, and obtaining suspension after quenching; the temperature during quenching is 0-10 ℃, and the pH value during quenching is adjusted to 9.5-11.0;
II) directly adding acid into the suspension for neutralization until the pH value is 6.5-7.5, and filtering after neutralization to obtain filter residue and filtrate containing sucralose-6-acetate.
2. The improved post-treatment method of sucralose chlorination solution according to claim 1, wherein in step I), the weak base is ammonia water, and the pH is adjusted to 9.5-11.0 during quenching and kept for half an hour.
3. The improved sucralose chlorination solution post-treatment method of claim 2, wherein: the pH value is preferably 10.0 to 10.5 at the time of quenching.
4. An improved sucralose chlorination solution post-treatment method according to claim 1, 2 or 3, wherein the acid used for neutralization is hydrochloric acid, and the pH value during neutralization is preferably 7.0-7.5.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112292385A (en) * | 2020-09-18 | 2021-01-29 | 安徽金禾实业股份有限公司 | Post-treatment method of sucrose-6-carboxylate chlorination reaction liquid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060205936A1 (en) * | 2005-03-14 | 2006-09-14 | Sl Laboratories, Llc | Chlorination of Sucrose-6-esters |
| CN102070678A (en) * | 2010-12-31 | 2011-05-25 | 常州市牛塘化工厂有限公司 | Preparation method of trichlorosucrose-6-acetate |
| CN108047283A (en) * | 2018-01-10 | 2018-05-18 | 福建科宏生物工程股份有限公司 | The method for subsequent processing of chlorination in a kind of Sucralose production |
| CN110563777A (en) * | 2019-08-30 | 2019-12-13 | 山东新和成精化科技有限公司 | method for post-treating sucralose chlorination liquid |
-
2020
- 2020-05-22 CN CN202010439212.5A patent/CN111548375A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060205936A1 (en) * | 2005-03-14 | 2006-09-14 | Sl Laboratories, Llc | Chlorination of Sucrose-6-esters |
| CN102070678A (en) * | 2010-12-31 | 2011-05-25 | 常州市牛塘化工厂有限公司 | Preparation method of trichlorosucrose-6-acetate |
| CN108047283A (en) * | 2018-01-10 | 2018-05-18 | 福建科宏生物工程股份有限公司 | The method for subsequent processing of chlorination in a kind of Sucralose production |
| CN110563777A (en) * | 2019-08-30 | 2019-12-13 | 山东新和成精化科技有限公司 | method for post-treating sucralose chlorination liquid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112292385A (en) * | 2020-09-18 | 2021-01-29 | 安徽金禾实业股份有限公司 | Post-treatment method of sucrose-6-carboxylate chlorination reaction liquid |
| WO2022056840A1 (en) * | 2020-09-18 | 2022-03-24 | 安徽金禾实业股份有限公司 | Post-treatment method of sucrose-6-carboxylic ester chlorination reaction liquid |
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