CN114106065A - Method for directly preparing sucralose by sucralose chlorination liquid - Google Patents
Method for directly preparing sucralose by sucralose chlorination liquid Download PDFInfo
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Abstract
The invention relates to a method for directly preparing sucralose by sucralose chlorination liquid, which is characterized by comprising the following steps: (1) adding alkali into a chlorination solution for neutralization, controlling the temperature to be-10-30 ℃, reacting for 0.5-4 h under the condition that the pH is = 7-9, and adjusting the pH to be 6-7 by using acid; (2) concentrating to recover solvent, adding water into the concentrate, and distilling again to obtain concentrated dry substance; (3) adding water, an organic solvent I and hydrogen peroxide to carry out oxidation reaction; the mass ratio of concentrated dry matter, water, organic solvent I and hydrogen peroxide is = 1: 0.1-3: 1-20: 0.1-2, adjusting the pH to be 7.0-9.0 by using alkali, reacting for 1-72 hours, and adjusting the pH to be 6-7; (4) standing for layering, and performing thermal extraction on the water phase for multiple times by using an organic solvent; concentrating the organic phase; (5) adding water and organic solvent I into the concentrated dry matter, dissolving, concentrating, adding organic solvent II and alkali solution, and performing deacetylation reaction. The invention has the advantages that: the reaction yield of the second step is improved from below 50 percent to 60 to 75 percent, and the yield of the sucralose is improved from 40 to 45 percent to 45 to 65 percent; the amount of carbon residue produced is reduced and the amount of waste liquid is reduced.
Description
Technical Field
The invention belongs to the technical field of sucralose production, and relates to a method for directly preparing sucralose from sucralose chlorination liquid.
Background
Sucralose (TGS), a novel sweetener developed by the british tare company (Tate & Lyle) together with university of london and patented in 1976; the sugar-free functional sweetener is a functional sweetener only taking sucrose as a raw material, the original trade name is Splenda, and the sweetness can reach 600 times that of the sucrose. The sweetener has the characteristics of no energy, high sweetness, pure sweetness, high safety and the like, and is one of the most excellent functional sweeteners at present.
The industrial production of sucralose basically adopts a monoester method, i.e. sucrose-6-carboxylate is prepared firstly, then a chlorinating agent (phosgene, solid phosgene, thionyl chloride, phosphorus trichloride, etc.) and DMF are adopted to form Vickers salt for chlorination reaction to obtain sucralose-6-carboxylate, and then the sucralose is prepared by alcoholysis.
At present, the synthesis process of sucralose can be divided into three main steps of reactions, namely acylation, chlorination and deacylation, but the total reaction yield of sucralose is generally 40-50%, and the yield is relatively low. Therefore, it is very urgent to develop a technique for reducing the loss and improving the yield.
Disclosure of Invention
The invention aims to solve the problem of low sucralose yield in the existing sucralose production, and provides a method for directly preparing sucralose by sucralose chlorination liquid.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for directly preparing sucralose by sucralose chlorination liquid comprises a neutralization step and a deacetylation step, and is characterized by comprising the following steps:
(1) adding alkali into a chlorination solution of sucrose-6-ester for neutralization, controlling the neutralization temperature to be-10-30 ℃, reacting for 0.5-4 h under the pH condition when the pH of the solution reaches 7-9, and then adjusting the pH to 6-7 by using acid to obtain a neutralization solution;
(2) distilling and concentrating the neutralized solution (40-80 ℃, the vacuum degree is 0.085-0.099 MPa), recovering trichloroethane and DMF, then adding water which is 0.5-10 times of the weight of the concentrate into the concentrate, distilling and concentrating again (40-75 ℃) to obtain a chlorinated solution neutralized and concentrated dry substance, and recovering DMF in the chlorinated solution;
the water is added, distillation and concentration can be carried out repeatedly for multiple times (2-5) according to actual conditions, otherwise, the residual DMF is unfavorable for the post-treatment of the concentrate (DMF can react with the subsequent oxidant hydrogen peroxide, hydrogen peroxide is consumed, byproducts can influence the subsequent separation and extraction, and even sucralose-6-ester can be severely damaged by the reaction, so that bumping and danger can be caused seriously);
(3) adding water, an organic solvent I and hydrogen peroxide into the neutralized and concentrated dry substance of the chlorination solution for oxidation reaction; controlling the mass ratio of the concentrated dry matter, water, the organic solvent I and hydrogen peroxide to be 1: 0.1-3: 1-20: 0.1-2, adjusting the pH value to 7.0-9.0 by using alkali, carrying out oxidation reaction for 1-72 hours under the condition of the pH value, and then adjusting the pH value to 6-7 by using acid;
(4) after the oxidation reaction is finished, standing and layering the oxidation solution, separating an upper organic phase and a lower aqueous phase, carrying out heat extraction on the aqueous phase for more than 3 times (10-80 ℃) by using an organic solvent, and combining all organic phases; concentrating the organic phase, controlling the concentration temperature to be 30-80 ℃, the vacuum degree to be 0.075-0.099 MPa and the concentration time to be 1 min-24 h to obtain an oxidized concentrated dry substance;
(5) adding water with the mass of 0.1-5 times and organic solvent with the mass of 1-20 times into the oxidized concentrated dry matter (mainly sugars of sucralose-6-ester, the content of the sugars is 10-30%) to dissolve and extract various sugars, and removing a small amount of waste salt; heating and concentrating the organic extraction solution, and distilling out the organic solvent to obtain a concentrated dry substance of the sucralose-6-ester saccharides;
(6) adding an organic solvent II and an alkali solution with the mass of 0.1-5 times of the concentrated dry substance into the concentrated dry substance of the saccharides of the sucralose-6-ester for deacetylation reaction.
Further, the alkali adopted in the neutralization step in the step (1) is one of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate or ammonia water, and preferably sodium hydroxide.
Further, the concentration of the alkali in the step (1) is 5-45%.
Further, the acid adopted in the step (1) neutralization step is one of hydrochloric acid, acetic acid, sulfuric acid or phosphoric acid, and hydrochloric acid is preferred.
Further, in the step (3), the organic solvent one is one of ethyl acetate, methyl acetate, propyl acetate, butyl acetate, dichloromethane, trichloroethane, toluene or cyclohexane, and preferably ethyl acetate.
Further, in the step (3), the alkali is one of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate or ammonia water, and preferably sodium hydroxide.
Further, in the step (6), the organic solvent II is one of methanol, ethanol, acetonitrile, tetrahydrofuran, dioxane or isopropanol, and preferably methanol.
Further, in the step (6), the alkali is one of sodium hydroxide, sodium carbonate or sodium methoxide, preferably sodium hydroxide, and the concentration is 5-45%.
The inventor finds that: in three major steps of reactions (acylation, chlorination and deacylation reactions) of sucralose, the yields of the first step and the third step are basically over 85 percent, and even over 90 percent after the process is optimized; the yield of the second reaction step is usually below 50%; namely, the low yield of the chlorination reaction in the second step is a key step for limiting the yield of the sucralose; and further research finds that: the reasons for the low yield of the second chlorination reaction mainly include the following three points: firstly, in the neutralization process of chlorination reaction liquid, when the PH is neutralized to be more than 9, a large amount of carbon residue (accounting for 5-25% of the total sugar) is generated; secondly, part of the sucralose-6-carboxylate can form a sulfite compound byproduct with thionyl chloride and DMF (dimethyl formamide), so that the compound byproduct can not be hydrolyzed easily, and the compound byproduct can be retained in an organic solution (accounting for 5-20% of the total sugar) in the crystallization and purification process of the sucralose-6-ester; and thirdly, in the processes of extraction separation and crystallization purification of the salt and the sucralose-6-ester, part of the sucralose-6-ester and part of the byproduct sucralose are left in a salt water phase (accounting for 3-10% of the total sugar) and an organic solvent crystallization mother liquor (accounting for 20-40% of the total sugar). Thus leading to excessive losses, close to 50% overall, and therefore in practice the chlorination yield of the second step is generally around 50%.
The invention controls the following steps in a targeted manner, thereby improving the yield of the second step reaction and further improving the yield of the sucralose: firstly, strictly controlling the PH value in the neutralization process to reduce the formation of carbon slag; secondly, the sulfite structure is oxidized by hydrogen peroxide to form sulfate (easy to hydrolyze), so that more sucralose-6-ester is released; thirdly, all the sucralose-6-ester and the partially hydrolyzed sucralose are extracted from the brine by adopting a thermal extraction mode, and the hydrolyzed sucralose completely enters a deacetylation procedure without separation such as crystallization and purification, so that the hydrolyzed sucralose in the process is utilized to the maximum extent, the yield is improved, and the problems of carbon residue discharge and post-treatment are reduced.
The invention has the advantages that: by adopting the method, the reaction yield of the second step is improved to 60-75% from the original lower 50%, so that the yield of the sucralose is improved to 45-65% from the original 40-45%; meanwhile, the oxidation method of the invention directly prepares the sucralose, no carbon residue is generated, the waste liquid amount is reduced, the environmental protection cost is reduced, and the process is simpler.
Detailed Description
Example 1
(1) Adding 1000mL of sucrose-6-ester chlorination solution (obtained by chlorination reaction of 65g of sucrose-6-ester raw material) into a 2000mL four-neck flask, stirring in an ice water bath, dropwise adding 20% ammonia water (230 mL) to neutralize until the pH is =8.5, stirring for reaction for 1h, adjusting the pH to be =6.5 by using 10% hydrochloric acid, and continuing stirring for 2h to obtain a neutralization solution;
(2) distilling and concentrating the neutralized solution (60 deg.C, vacuum degree of 0.09 MPa) for 60min, recovering trichloroethane and DMF 900L, adding 500mL of water into the concentrate, distilling and concentrating (70 deg.C) for 1h, adding 500mL of water again, continuing distilling and concentrating (70 deg.C) for 1h, and recovering DMF 80mL to obtain neutralized and concentrated product of chlorinated solution;
(3) adding 100mL of water and 1000mL of ethyl acetate into 150 g of chlorinated solution neutralized concentrated dry matter, stirring for dissolving, transferring to a 2000mL four-neck flask, stirring in an ice water bath, dropwise adding 60mL of 30% hydrogen peroxide, slowly dropwise adding 20% ammonia water, controlling the pH =8, maintaining the pH for stirring reaction for 48 hours until the color of the solution is changed from brown black to brown yellow, and adjusting the pH =6.5 by using 10% hydrochloric acid;
(4) after the oxidation reaction is finished, standing and layering the oxidation solution, separating an upper organic phase 1700L and a lower aqueous phase 350L, extracting the aqueous phase 10 times by using 2000mL ethyl acetate at the temperature of 50 ℃, and combining all organic phases; concentrating the organic phase, controlling the concentration temperature at 50 ℃, the vacuum degree at 0.085MPa and the concentration time at 2h to obtain an oxidized concentrated dry substance;
(5) 80g of the oxidized concentrated substance was added to the flask, 250mL of methanol was added to dissolve each saccharide, 10% sodium methoxide in methanol (20L) was added dropwise in a low-temperature ice-water bath, pH =9 was adjusted, the reaction was stirred for 1 hour with the pH maintained, and the pH was adjusted to =6.5 with 10% hydrochloric acid, and 95g of a crude sucralose mixture was obtained after distilling off the methanol.
Purification of a crude mixture of sucralose:
a. dissolving 95g of the primary product mixture of the sucralose by stirring with 150mL of water, transferring the mixture to a 1000mL glass separating funnel, firstly adding 100mL of butyl acetate to extract and remove small polar impurities, then extracting the sucralose by 5 times with 1000mL of ethyl acetate, and combining ethyl acetate phases;
b. heating the ethyl acetate phase to 60 ℃, evaporating the organic solvent, adding 200mL of butyl acetate, stirring strongly and pulping to form a suspension of powdery crystal sucralose and the butyl acetate phase; under the condition of stirring, the primary sucralose product mixture suspension is subjected to gradient cooling to 0 ℃ and kept for 12 hours to obtain sucralose crystal slurry with better crystallization performance; filtering and drying to obtain 46g of crude sucralose powder crystal product, wherein the purity of the crude sucralose powder crystal product exceeds 97 percent, and the total yield of chlorination reaction and deacetylation reaction is 65 percent;
c. and (b) washing the filtered ethyl acetate phase crystallization mother liquor with 50mL of pure water, recovering the sucralose (about 15 g) in the mother liquor, and directly dissolving the primary product mixture in the step a by using the washing water containing the recovered sucralose, so that the recovery and reuse are realized and the yield is improved.
Taking 46g of crude sucralose product, heating to 50 ℃ by using 100mL of ultrapure water, stirring for dissolving, adding 5g of activated carbon for decolorization, filtering and purifying the solution by using a precision pipeline filter, carrying out countercurrent extraction and impurity removal by using 100mL of isopropyl acetate, carrying out standing for liquid separation, carrying out pressure reduction and concentration on a water phase, concentrating until the solid content is about 60%, carrying out program cooling to 20 ℃ to obtain a large amount of sucralose crystals, centrifuging, washing with a small amount of cold ultrapure water to obtain wet sucralose, drying to obtain 30g of high-purity sucralose crystals, and measuring the purity of the sucralose crystals with HPLC (high performance liquid chromatography) of 99.98% to obtain qualified sucralose crystals.
Example 2
(1) Adding 1000mL of sucrose-6-ester chlorination solution (obtained by chlorination reaction of 65g of sucrose-6-ester raw material) into a 2000mL four-neck flask, stirring in an ice water bath, dropwise adding 20% ammonia water (250 mL) to neutralize until the pH is =8.0, stirring for reaction for 1h, adjusting the pH to be =6.5 by using 10% hydrochloric acid, and continuing stirring for 2h to obtain a neutralization solution;
(2) distilling and concentrating the neutralized solution (75 deg.C, vacuum degree of 0.095 MPa) for 240min, recovering trichloroethane and DMF 750mL, adding 500mL water into the concentrate, distilling and concentrating (70 deg.C) for 1h, adding 500mL water again, continuing distilling and concentrating (70 deg.C) for 1h, and recovering DMF 90mL to obtain neutralized and concentrated dry product of chlorinated solution;
(3) adding 100mL of water and 1000mL of ethyl acetate into 160g of chlorinated solution neutralized concentrated dry matter, stirring for dissolving, transferring to a 2000mL four-neck flask, stirring in an ice water bath, dropwise adding 60mL of 30% hydrogen peroxide, slowly dropwise adding 20% ammonia water, controlling the pH =8, maintaining the pH stirring for reaction for 36 hours until the color of the solution is changed from brown black to brown yellow, and adjusting the pH =6.5 by using 10% hydrochloric acid;
(4) after the oxidation reaction is finished, standing and layering the oxidation solution, separating 400 mL of an upper organic phase and 800L of a lower water phase, extracting the water phase for 10 times by using 2000mL of ethyl acetate at the temperature of 50 ℃, and combining all organic phases; concentrating the organic phase, controlling the concentration temperature at 55 ℃, the vacuum degree at 0.09MPa and the concentration time at 10h to obtain an oxidized concentrated dry substance;
(5) adding 250mL of methanol into 90g of the flask oxidation concentrated dry matter to dissolve and extract various saccharides and removing a small amount of waste salt; subsequently, a 40% NaOH solution (about 60 mL) was added to maintain the pH at =9, the reaction was stirred for 2 hours, the pH was adjusted to =6.5 with 10% HCl, and 110g of a crude sucralose mixture was obtained after distilling off methanol.
Purification of a crude mixture of sucralose:
a. dissolving 110g of a primary product mixture of sucralose by using 250mL of water through stirring, transferring the mixture into a 1000mL glass separating funnel, firstly adding 50mL of butyl acetate to extract and remove small-polarity impurities, then extracting the sucralose by using 1000mL of ethyl acetate for 5 times, and combining ethyl acetate phases;
b. heating the ethyl acetate phase to 60 ℃, evaporating the organic solvent, adding 200mL of butyl acetate, stirring and pulping by strong force to form a suspension of powdery crystal sucralose and the butyl acetate phase; under the condition of stirring, the primary sucralose product mixture suspension is subjected to gradient cooling to 10 ℃ and kept for 12 hours to obtain sucralose crystal slurry with better crystallization performance; 53g of crude sucralose powder crystal product is obtained after filtration and drying, the purity is over 97 percent, and the total yield of chlorination reaction and deacetylation reaction is 75 percent.
Example 3
The experimental procedure was as in example 1, and the crude sucralose powder crystals (48 g) were obtained from the neutralization of ammonia with chloride solution, the oxidation of ammonia with oxide, and the deacetylation of NaOH, with a purity of over 97%, and a total yield of 68% for the chlorination and deacetylation reactions.
Example 4
The procedure was as in example 2, ammonia was used for neutralization of the chlorination solution, and NaOH was used for oxidation and deacetylation to obtain 49g of crude sucralose powder crystals with a purity of over 97% and a total yield of chlorination and deacetylation of 69%.
Example 5
The experimental procedure was as in example 2, and the chlorination solution neutralized NaOH for oxidation and sodium methoxide for deacetylation to obtain 51g of crude sucralose powder crystal with purity over 97% and total yield of chlorination and deacetylation 72%.
Comparative example 1
(1) Adding 1000mL of sucrose-6-ester chlorination solution (obtained by chlorination reaction of 65g of sucrose-6-ester raw material) into a 2000mL four-neck flask, stirring in an ice water bath, dropwise adding 20% ammonia water (230 mL) to neutralize until the pH is =9.5, stirring for reaction for 1h, adjusting the pH to be =6.5 by using 10% hydrochloric acid, and continuing stirring for 2h to obtain a neutralization solution;
(2) distilling and concentrating the neutralized solution (60 deg.C, vacuum degree of 0.09 MPa) for 240min, recovering trichloroethane and DMF 750L, adding 500mL of water into the concentrate, distilling and concentrating (70 deg.C) for 1h, adding 500mL of water again, continuing distilling and concentrating (70 deg.C) for 1h, and recovering DMF 100L to obtain neutralized and concentrated dry product of the chlorinated solution;
(3) adding 2000mL of water into 180g of chlorination solution and the concentrated dry substance, heating and dissolving, pouring out supernatant, heating and stirring with 500mL of ethyl acetate for dissolving, standing at low temperature (10 ℃), crystallizing a large amount of solid, performing suction filtration and drying to obtain 40g of sucralose-6-ester, filtering mother liquor, concentrating, and continuing to crystallize to obtain 10g of sucralose-6-ester;
(4) 50g of the combined sucralose-6-ester is dissolved in 200mL of methanol, stirred in an ice-water bath, and added dropwise with a 10% sodium methoxide methanol solution, the pH is controlled at 9, the reaction is carried out while maintaining the pH under stirring for 1 hour, the pH is adjusted back to 6.5 with 10% hydrochloric acid, and 100g of a sucralose initial product mixture is obtained after distilling off the methanol.
Purification of a crude mixture of sucralose:
a. dissolving 100g of a primary product mixture of sucralose by using 250mL of water through stirring, transferring the mixture into a 1000mL glass separating funnel, firstly adding 100mL of butyl acetate to extract and remove small-polarity impurities, then extracting the sucralose by using 1000mL of ethyl acetate for 5 times, and combining ethyl acetate phases;
b. heating the ethyl acetate phase to 60 ℃, evaporating the organic solvent, adding 200mL of butyl acetate, stirring and pulping by strong force to form a suspension of powdery crystal sucralose and the butyl acetate phase; under the condition of stirring, the primary sucralose product mixture suspension is subjected to gradient cooling to 0 ℃ and kept for 12 hours to obtain sucralose crystal slurry with better crystallization performance; after filtration and drying, 31g of crude sucralose powder crystal product is obtained, the purity is over 97 percent, and the total yield of chlorination reaction and deacetylation reaction is 44 percent.
Comparative example 2
(1) Adding 1000mL of sucrose-6-ester chlorination solution (obtained by chlorination reaction of 65g of sucrose-6-ester raw material) into a 2000mL four-neck flask, stirring in an ice water bath, dropwise adding 20% ammonia water (250 mL) to neutralize until the pH is =8.0, stirring for reaction for 1h, adjusting the pH to be =6.5 by using 10% hydrochloric acid, and continuing stirring for 2h to obtain a neutralization solution;
(2) distilling and concentrating the neutralized solution (75 deg.C, vacuum degree of 0.095 MPa) for 240min, recovering trichloroethane and DMF 750L, adding 500mL of water into the concentrate, distilling and concentrating (70 deg.C) for 1h, adding 500mL of water again, continuing distilling and concentrating (70 deg.C) for 1h, and recovering DMF 100L to obtain neutralized and concentrated dry product of chlorinated solution;
(3) adding 2000mL of water into 190 g of chlorinated solution neutralized concentrated dry matter for dissolving, pouring out supernatant, extracting liquid by using 500mL of ethyl acetate, extracting water phase by using 500mL of ethyl acetate for 5 times, combining ethyl acetate phases, distilling and concentrating to obtain sugar concentrate of sucralose-6-ester, wherein the sugar concentrate contains 56g of sucralose-6-ester;
(4) 100g of the obtained sucrose concentrate of sucralose-6-ester was dissolved in 250mL of methanol, stirred in an ice-water bath, and a 10% sodium methoxide solution in methanol was added dropwise thereto while maintaining the pH =9, and the reaction was carried out for 1 hour with stirring, and then the pH =6.5 was adjusted with 10% hydrochloric acid, and 100g of a crude sucralose mixture was obtained after distilling off the methanol.
Purification of a crude mixture of sucralose:
a. dissolving 100g of a primary product mixture of sucralose by using 250mL of water through stirring, transferring the mixture into a 1000mL glass separating funnel, firstly adding 100mL of butyl acetate to extract and remove small-polarity impurities, then extracting the sucralose by using 1000mL of ethyl acetate for 5 times, and combining ethyl acetate phases;
b. heating the ethyl acetate phase to 60 ℃, evaporating the organic solvent, adding 200mL of butyl acetate, stirring and pulping by strong force to form a suspension of powdery crystal sucralose and the butyl acetate phase; under the condition of stirring, the primary sucralose product mixture suspension is subjected to gradient cooling to 0 ℃ and kept for 12 hours to obtain sucralose crystal slurry with better crystallization performance; after filtration and drying, 45g of crude sucralose powder crystal product is obtained, the purity is over 97 percent, and the total yield of chlorination reaction and deacetylation reaction is 60 percent.
Compared with the existing widely-used sucralose-6-ester extraction, crystallization and purification process, the oxidation method for directly preparing sucralose is provided, the process of filtering and removing carbon residue from the chlorinated common-mixed concentrated dry solution is not needed, the process of extracting, crystallization and purification of sucralose-6-ester is also removed, sulfite in the system is oxidized through the system oxidation, and raw materials for forming carbon residue and sucralose as a byproduct in the water phase are fully utilized, so that the problems of low yield of sucralose production, high impurity content in mother liquor, difficult separation, high production cost, difficult clean production and the like are solved, or at least partially solved. The method has the advantages of simplified process, simple and convenient operation, high production yield, low production cost, low impurity content of the mother liquor, easy treatment and the like, and has important value for the high-efficiency, energy-saving and environment-friendly production of the sucralose.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; those skilled in the art can make numerous possible variations and modifications to the present teachings, or modify equivalent embodiments to equivalent variations, without departing from the scope of the present teachings, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (9)
1. A method for directly preparing sucralose by sucralose chlorination liquid comprises a neutralization step and a deacetylation step, and is characterized by comprising the following steps:
(1) adding alkali into a chlorination solution of sucrose-6-ester for neutralization, controlling the neutralization temperature to be-10-30 ℃, reacting for 0.5-4 h under the pH condition when the pH of the solution reaches 7-9, and then adjusting the pH to 6-7 by using acid to obtain a neutralization solution;
(2) distilling and concentrating the neutralized solution, recovering trichloroethane and DMF, adding water with the weight of 0.5-10 times of that of the concentrate into the concentrate, distilling and concentrating again to obtain a chlorinated solution neutralized dry substance, and recovering DMF in the chlorinated solution;
(3) adding water, an organic solvent I and hydrogen peroxide into the neutralized and concentrated dry substance of the chlorination solution for oxidation reaction; controlling the mass ratio of the concentrated dry matter, water, the organic solvent I and hydrogen peroxide to be 1: 0.1-3: 1-20: 0.1-2, adjusting the pH value to 7.0-9.0 by using alkali, carrying out oxidation reaction for 1-72 hours under the condition of the pH value, and then adjusting the pH value to 6-7 by using acid;
(4) after the oxidation reaction is finished, standing and layering the oxidation solution, separating an upper organic phase and a lower aqueous phase, carrying out repeated thermal extraction on the aqueous phase by using an organic solvent, and combining all organic phases; concentrating the organic phase, controlling the concentration temperature to be 30-80 ℃, the vacuum degree to be 0.075-0.099 MPa and the concentration time to be 1 min-24 h to obtain an oxidized concentrated dry substance;
(5) adding water with the mass of 0.1-5 times and organic solvent with the mass of 1-20 times of the mass of the concentrated dry matter into the oxidized concentrated dry matter for dissolving and extracting various saccharides, and removing a small amount of waste salt; heating and concentrating the organic solution, and distilling out the organic solvent to obtain a concentrated dry substance of the sugar of the sucralose-6-ester;
(6) adding an organic solvent II and an alkali solution with the mass of 0.1-5 times of the concentrated dry substance into the concentrated dry substance of the saccharides of the sucralose-6-ester for deacetylation reaction.
2. The method of claim 1, wherein the sucralose chlorination solution is used for directly preparing sucralose, and the method comprises the following steps: the alkali adopted in the neutralization step in the step (1) is one of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate or ammonia water.
3. The method for directly preparing sucralose from a sucralose chlorination solution according to claim 1 or 2, wherein: the concentration of the alkali in the step (1) is 5-45%.
4. The method of claim 1, wherein the sucralose chlorination solution is used for directly preparing sucralose, and the method comprises the following steps: the acid adopted in the neutralization step in the step (1) is one of hydrochloric acid, acetic acid, sulfuric acid or phosphoric acid.
5. The method of claim 1, wherein the sucralose chlorination solution is used for directly preparing sucralose, and the method comprises the following steps: and (3) the first organic solvent is one of ethyl acetate, methyl acetate, propyl acetate, butyl acetate, dichloromethane, trichloroethane, toluene or cyclohexane.
6. The method for directly preparing sucralose from the sucralose chlorination solution according to claim 1, 2, 4 or 5, wherein: and (3) the alkali is one of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate or ammonia water.
7. The method for directly preparing sucralose from the sucralose chlorination solution according to claim 1, 2, 4 or 5, wherein: the temperature of the heat extraction in the step (4) is 10-80 ℃.
8. The method for directly preparing sucralose from the sucralose chlorination solution according to claim 1, 2, 4 or 5, wherein: and (3) in the step (6), the organic solvent II is one of methanol, ethanol, acetonitrile, tetrahydrofuran, dioxane or isopropanol.
9. The method for directly preparing sucralose from the sucralose chlorination solution according to claim 1, 2, 4 or 5, wherein: and (3) in the step (6), the alkali is one of sodium hydroxide, sodium carbonate or sodium methoxide, and the concentration is 5-45%.
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|---|---|---|---|---|
| CN116568695A (en) * | 2023-02-27 | 2023-08-08 | 安徽金禾实业股份有限公司 | Method for treating crude sugar in chlorination neutralization solution of sucralose-6-ester |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101270136A (en) * | 2007-03-22 | 2008-09-24 | 常州市牛塘化工厂有限公司 | Process for preparing sucrose trichloride-6-ester |
| CN102321122A (en) * | 2011-10-21 | 2012-01-18 | 湖北益泰药业有限公司 | Method for preparing sucralose from sucralose-6-acetate |
| CN104774227A (en) * | 2015-04-08 | 2015-07-15 | 常州市牛塘化工厂有限公司 | Chlorination method for sucrose-6-ethyl ester |
| CN105131050A (en) * | 2015-07-22 | 2015-12-09 | 青岛科技大学 | Preparation method of chlorinating agent and method therewith for preparing sucralose |
| CN109467578A (en) * | 2018-03-14 | 2019-03-15 | 刘静 | A method of extracting Sucralose in multiple mother liquor |
| CN110563780A (en) * | 2019-08-30 | 2019-12-13 | 山东新和成精化科技有限公司 | Post-treatment method of sucralose chlorination liquid and application of sucralose chlorination liquid in preparation of sucralose |
| CN113677689A (en) * | 2021-07-07 | 2021-11-19 | 安徽金禾实业股份有限公司 | Method for purifying sucralose-6-ester |
| CN113717237A (en) * | 2021-08-17 | 2021-11-30 | 安徽金禾实业股份有限公司 | Method for preparing sucralose from sucralose-6-acetate neutralization solution |
-
2021
- 2021-12-20 CN CN202111561142.1A patent/CN114106065A/en not_active Withdrawn
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101270136A (en) * | 2007-03-22 | 2008-09-24 | 常州市牛塘化工厂有限公司 | Process for preparing sucrose trichloride-6-ester |
| CN102321122A (en) * | 2011-10-21 | 2012-01-18 | 湖北益泰药业有限公司 | Method for preparing sucralose from sucralose-6-acetate |
| CN104774227A (en) * | 2015-04-08 | 2015-07-15 | 常州市牛塘化工厂有限公司 | Chlorination method for sucrose-6-ethyl ester |
| CN105131050A (en) * | 2015-07-22 | 2015-12-09 | 青岛科技大学 | Preparation method of chlorinating agent and method therewith for preparing sucralose |
| CN109467578A (en) * | 2018-03-14 | 2019-03-15 | 刘静 | A method of extracting Sucralose in multiple mother liquor |
| CN110563780A (en) * | 2019-08-30 | 2019-12-13 | 山东新和成精化科技有限公司 | Post-treatment method of sucralose chlorination liquid and application of sucralose chlorination liquid in preparation of sucralose |
| CN113677689A (en) * | 2021-07-07 | 2021-11-19 | 安徽金禾实业股份有限公司 | Method for purifying sucralose-6-ester |
| CN113717237A (en) * | 2021-08-17 | 2021-11-30 | 安徽金禾实业股份有限公司 | Method for preparing sucralose from sucralose-6-acetate neutralization solution |
Non-Patent Citations (2)
| Title |
|---|
| CHENGJIN WANG, ET AL.: ""Full-scale comparison of UV-H2O2 and UV/Cl2 advanced oxidation: The degradation of micropollutant surrogates and the formation of disinfection byproducts"", 《WATER RESEARCH》 * |
| 蓝姗姗 等: ""三氯蔗糖-6-乙酸酯的分离与提纯"", 《中国食品添加剂-开发应用》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116568695A (en) * | 2023-02-27 | 2023-08-08 | 安徽金禾实业股份有限公司 | Method for treating crude sugar in chlorination neutralization solution of sucralose-6-ester |
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