CN116568695A - Method for treating crude sugar in chlorination neutralization solution of sucralose-6-ester - Google Patents
Method for treating crude sugar in chlorination neutralization solution of sucralose-6-ester Download PDFInfo
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- CN116568695A CN116568695A CN202380008493.0A CN202380008493A CN116568695A CN 116568695 A CN116568695 A CN 116568695A CN 202380008493 A CN202380008493 A CN 202380008493A CN 116568695 A CN116568695 A CN 116568695A
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- 238000006386 neutralization reaction Methods 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000007788 liquid Substances 0.000 claims abstract description 61
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002351 wastewater Substances 0.000 claims abstract description 33
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 17
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002699 waste material Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 93
- 150000002148 esters Chemical class 0.000 claims description 25
- 238000001179 sorption measurement Methods 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 19
- 239000012452 mother liquor Substances 0.000 claims description 18
- 239000008346 aqueous phase Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 238000004321 preservation Methods 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- 239000012071 phase Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 14
- 238000004094 preconcentration Methods 0.000 claims description 12
- 241000242583 Scyphozoa Species 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 8
- 239000002893 slag Substances 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 7
- 229960001701 chloroform Drugs 0.000 claims description 6
- 238000004042 decolorization Methods 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 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 abstract description 24
- 235000019408 sucralose Nutrition 0.000 abstract description 24
- 239000004376 Sucralose Substances 0.000 abstract description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000605 extraction Methods 0.000 abstract description 9
- 239000003960 organic solvent Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000005904 alkaline hydrolysis reaction Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 84
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000003825 pressing Methods 0.000 description 17
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000003756 stirring Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 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 5
- 238000010586 diagram Methods 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 229930006000 Sucrose Natural products 0.000 description 4
- 239000005720 sucrose Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000003381 deacetylation reaction Methods 0.000 description 3
- 238000005947 deacylation reaction Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012320 chlorinating reagent Substances 0.000 description 2
- 230000006196 deacetylation Effects 0.000 description 2
- SPJQBGGHUDNAIC-UHFFFAOYSA-N methyl 2,5-dichlorobenzoate Chemical compound COC(=O)C1=CC(Cl)=CC=C1Cl SPJQBGGHUDNAIC-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical group OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- FACOTAQCKSDLDE-YKEUTPDRSA-N [(2R,3R,4R,5R,6R)-6-[(2R,3S,4S,5S)-2,5-bis(chloromethyl)-3,4-dihydroxyoxolan-2-yl]oxy-3-chloro-4,5-dihydroxyoxan-2-yl]methyl acetate Chemical compound O[C@@H]1[C@@H](O)[C@@H](Cl)[C@@H](COC(=O)C)O[C@@H]1O[C@@]1(CCl)[C@@H](O)[C@H](O)[C@@H](CCl)O1 FACOTAQCKSDLDE-YKEUTPDRSA-N 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 208000026106 cerebrovascular disease Diseases 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- -1 sodium alkoxide Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 235000012773 waffles Nutrition 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Saccharide Compounds (AREA)
Abstract
The invention provides a method for treating crude sugar in a chlorination neutralization solution of sucralose-6-ester, and relates to the technical field of sucralose production. According to the invention, by recovering chloroform first and then DMF, the impurity content in the obtained concentrated dry liquid is obviously reduced, and the yield and purity of the obtained crude sugar are improved; the invention uses weak alkaline ammonia water to adjust the pH value of the system to 6-9, thereby avoiding the generation of the sucralose by alkaline hydrolysis of the sucralose-6-ester caused by too strong alkalinity and improving the yield and purity of crude sugar. In addition, the method does not need to consume a large amount of acid, hydrogen peroxide, organic solvent (oxidation reaction stage) and heat energy (multiple times of heat extraction), and the treatment cost of the chlorination neutralization solution is low. In addition, the treatment method provided by the invention can improve the conversion rate and daily productivity of the sucralose-6-ester in the chlorination neutralization liquid, reduce the production amount of wastewater and waste activated carbon, and has the advantages of less three wastes, low energy consumption and low production cost.
Description
Technical Field
The invention relates to the technical field of sucralose production, in particular to a method for treating crude sugar in a chlorination neutralization solution of sucralose-6-ester.
Background
Sucralose, commonly called sucralose, is white crystal powder or granule in appearance, is a new generation sweetener which takes sucrose as raw material, has sweetness 600 times that of sucrose, pure taste and no participation in metabolism of human body, can be used for 'zero calorie' sugar for diabetics, cardiovascular and cerebrovascular disease patients and the elderly, has the characteristics of good stability, high safety and the like, and is widely applied to a plurality of fields of food, beverage, daily chemicals, medicines and the like.
Currently, the production process of sucralose mainly comprises the following five steps of reactions: (1) acylation reaction: taking sucrose as a raw material, N, N-Dimethylformamide (DMF) as a solvent, organic tin as a catalyst, acetic anhydride as an acylating agent for reaction, and taking sucrose-6-ethyl ester as a reaction product; (2) Chlorination: taking sucrose-6-ethyl ester as a raw material, taking DMF and trichloroethane as solvents, carrying out chlorination reaction under the action of a chlorinating agent (a waffle reagent or phosgene), neutralizing the obtained chlorinated solution by using liquid alkali or ammonia water, evaporating the obtained chlorinated neutralized solution to recover the solvents DMF and trichloroethane, adding water for dissolution, and carrying out treatment steps such as multistage separation and purification to obtain a pure trichlorosucrose-6-acetate product; (3) deacylation reaction: the method is characterized in that high-purity sucralose-6-acetate is used as a raw material, an alkaline reagent (such as hydroxide and sodium alkoxide) is used as a catalyst, methanol is used as a solvent, deacylation reaction is carried out, and separation and purification are carried out, so that a pure sucralose product is obtained. Among them, the yields of the acylation and deacylation reaction are 85% or more, the yield of the chlorination reaction is usually 50% or less, and it is seen that the low yield of the chlorination reaction is a key step of limiting the yield of sucralose.
Chinese patent CN114106065a discloses a method for directly preparing sucralose from sucralose chlorination solution, which comprises a neutralization step and a deacetylation step, and specifically comprises the following steps: (1) Adding alkali into the chloridizing solution of sucrose-6-ester to adjust the pH to 7-9 for neutralization, and then adjusting the pH to 6-7 by using acid to obtain a neutralization solution; (2) Distilling and concentrating the neutralization solution, recovering trichloroethane and DMF, adding water with the weight 0.5-10 times of the weight of the concentrate into the concentrate, distilling and concentrating again to obtain a neutralization concentrated dry matter of the chlorinated solution, and recovering DMF; (3) Adding water, organic solvent I (ester solvent, dichloromethane, chloroform) and hydrogen peroxide into the chloridized solution and the concentrated dry matter for oxidation reaction; then the pH value is regulated to 6 to 7 by acid; (4) After the oxidation reaction is finished, standing and layering the oxidation solution, separating an upper organic phase and a lower aqueous phase, repeatedly and thermally extracting the aqueous phase with an organic solvent for many times, and combining all the organic phases; concentrating the organic phase to obtain an oxidized concentrated dry matter; (5) Adding an organic solvent I into the oxidized concentrated dry matter to dissolve and extract various saccharides, and removing a small amount of waste salt; then heating and concentrating the organic solution, and distilling the organic solvent to obtain a concentrated dry matter of the saccharide of the sucralose-6-ester; (6) Adding an organic solvent II and an alkali solution into the concentrated dry matter of the saccharide of the sucralose-6-ester to carry out deacetylation reaction. This prior art improves the yield of sucralose by several means: 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 all the sucralose are subjected to deacetylation procedures without separation such as crystallization, purification and the like, so that the yield is improved, and the carbon residue emission and post-treatment problems are reduced. However, the chloridizing solution of the prior art sucralose-6-ester needs to be additionally added with hydrogen peroxide and an organic solvent for oxidation, needs to be added with acid for neutralization after oxidation reaction, and needs to be subjected to heat extraction for multiple times, so that a large amount of acid, hydrogen peroxide, the organic solvent (oxidation reaction stage) and heat energy are consumed, and the treatment cost of the chloridizing neutralization solution is high.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for treating crude sugar in a chlorination neutralization solution of sucralose-6-ester, which has the advantages of low cost and high yield of crude sugar.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for treating crude sugar in a chlorination neutralization solution of sucralose-6-ester, which is characterized by comprising the following steps:
(1) Pre-concentrating the chloridized neutralization solution of the sucralose-6-ester to recover the trichloromethane to obtain a pre-concentrated solution;
(2) Concentrating and preserving the pre-concentrate in sequence to recover N, N-dimethylformamide to obtain concentrated dry liquid;
(3) Mixing the concentrated dry liquid with activated carbon, regulating the pH value to 6-9 by using ammonia water, and carrying out solid-liquid separation after decolorization treatment to obtain decolorized liquid and adsorption activated carbon respectively;
(4) Mixing the decolorized solution, the ester extractant and the water phase, and cooling and crystallizing to obtain crude sugar; the aqueous phase comprises water and/or an ester-bound aqueous phase.
Preferably, in the step (1), the temperature of the pre-concentration is 30-65 ℃, the pressure is-99 to-90 kPa, and the volume of the pre-concentration solution is 60-70% of the volume of the chloridized neutralization solution of the sucralose-6-ester.
Preferably, in the step (2), the temperature of the concentration is 40-75 ℃ and the pressure is-99 to-80 kPa;
the temperature of the heat preservation is 60-65 ℃ and the time is 1-3 h.
Preferably, the water knot mother liquor or the mixed liquor of the water knot mother liquor and the wastewater is added in the concentration process;
the content of the sucralose-6-ester in the water knot mother liquor is 10-20 g/L;
the wastewater comprises at least one of activated carbon washing water, inorganic salt wastewater, adsorption wastewater, waste clear water and slag discharging water;
the volume ratio of the jellyfish liquid to the wastewater is 1.2-2: 1.8 to 3.
Preferably, in the step (3), the mass of the activated carbon is 0.5-2% of the mass of the concentrated dry liquid.
Preferably, in the step (3), the concentration of the ammonia water is 20 to 25wt%.
Preferably, in the step (3), the decolorizing treatment is performed at a temperature of 60-65 ℃ for 1-3 hours.
Preferably, in the step (4), the volume ratio of the decolorized solution to the ester extractant is 1:0.45 to 0.6;
the volume ratio of the decolorized solution to the water phase is 1:0.04 to 0.13.
Preferably, in the step (4), the temperature of the cooling crystallization is-3-10 ℃ and the time is 4-6 h.
The invention provides a method for treating crude sugar in a chlorination neutralization solution of sucralose-6-ester, which comprises the following steps: (1) Pre-concentrating the chloridized neutralization solution of the sucralose-6-ester to recover the trichloromethane to obtain a pre-concentrated solution; (2) Concentrating and preserving the pre-concentrate in sequence to recover N, N-Dimethylformamide (DMF) to obtain concentrated dry liquid; (3) Mixing the concentrated dry liquid with activated carbon, regulating the pH value to 6-9 by using ammonia water, and carrying out solid-liquid separation after decolorization treatment to obtain decolorized liquid and adsorption activated carbon respectively; (4) Mixing the decolorized solution, the ester extractant and the water phase, and cooling and crystallizing to obtain crude sugar; the aqueous phase comprises water and/or an ester-bound aqueous phase. In addition, the invention obviously reduces the impurity content in the obtained concentrated dry liquid by firstly recovering the trichloroethane and then recovering the DMF, and improves the yield and purity of the obtained crude sugar (B sugar); meanwhile, the trichloroethane obtained by recycling and the DMF obtained by recycling are high in purity and can be recycled in the production process of the trichlorosucrose; the invention uses weak alkaline ammonia water to adjust the pH value of the system to 6-9, thereby avoiding the generation of sucralose by alkaline hydrolysis of sucralose-6-ester due to strong alkalinity, improving the yield and purity of crude sugar in the chlorination neutralization liquid, improving the conversion rate of sucralose-6-ester in the chlorination neutralization liquid (from 38-42% to 48-52%), improving the daily capacity of sucralose-6-ester crude sugar (from 38-40 tons to 41-43 tons), and further reducing the waste water (7-8 m) 3 Down to 5-6 m 3 ) And waste active carbon (from original 12-15 tons to 10-12 tons), and has the advantages of less three wastes, low energy consumption and low production cost. In addition, the invention does not consume a large amount of acid, hydrogen peroxide and organic solvent (oxygenChemical reaction stage) and heat energy (multiple heat extraction), and the treatment cost of the chloridizing neutralization solution is low.
In addition, the treatment method provided by the invention has the advantages that the yield of crude sugar is above 60%, the purity is above 88%, and the yield and purity are high as shown in the test results of the examples.
Drawings
FIG. 1 is a flow chart of a process for treating a chlorination neutralization solution of sucralose-6-ester.
Detailed Description
The invention will be further described with reference to examples and figures.
The invention provides a method for treating crude sugar in a chlorination neutralization solution of sucralose-6-ester, which comprises the following steps:
(1) Pre-concentrating the chloridized neutralization solution of the sucralose-6-ester to recover the trichloromethane to obtain a pre-concentrated solution;
(2) Concentrating and preserving the pre-concentrate in sequence to recover N, N-dimethylformamide to obtain concentrated dry liquid;
(3) Mixing the concentrated dry liquid with activated carbon, regulating the pH value to 6-9 by using ammonia water, and carrying out solid-liquid separation after decolorization treatment to obtain decolorized liquid and adsorption activated carbon respectively;
(4) Mixing the decolorized solution, the ester extractant and the water phase, and cooling and crystallizing to obtain crude sugar; the aqueous phase comprises water and/or an ester-bound aqueous phase.
In the present invention, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise.
The invention pre-concentrates the chloridized neutralization solution of the sucralose-6-ester to recycle the trichloromethane, thus obtaining the pre-concentrated solution.
The method for preparing the chloridizing and neutralizing solution of the sucralose-6-ester is not particularly limited, and the chloridizing and neutralizing solution in the process of preparing the sucralose by taking the sucrose as an initial raw material, which is well known to a person skilled in the art, can be adopted, specifically, the method comprises the following steps: taking sucrose as a raw material, N, N-Dimethylformamide (DMF) as a solvent, acetic anhydride as an acylating agent and organic metal as a catalyst to prepare a solution containing sucrose-6-acetate; and then, using DMF and trichloroethane as solvents to carry out chlorination reaction under the action of a chlorinating agent, using ammonia water to carry out neutralization, and then using hydrochloric acid to adjust back the pH value to obtain a chlorination neutralization solution of the sucralose-6-ester. The specific conditions for preparing the chlorination neutralizing solution of sucralose-6-ester are not particularly limited, and the preparation conditions of the chlorination neutralizing solution of sucralose-6-ester, which are well known to those skilled in the art, may be employed.
In the present invention, the temperature of the pre-concentration is preferably 30 to 65 ℃, more preferably 40 to 60 ℃; the pressure of the pre-concentration is preferably-99 to-90 kPa, more preferably-97 to-93 kPa, and the time of the pre-concentration is not particularly limited in the present invention, and the volume of the pre-concentrated solution may be 60 to 70% (more preferably 64 to 65%) of the volume of the chlorinated neutralization solution of the sucralose-6-ester.
After the pre-concentrated solution is obtained, the pre-concentrated solution is concentrated and heat-preserved in sequence to recover N, N-dimethylformamide, so as to obtain concentrated dry solution.
In the present invention, the temperature of the concentration is preferably 40 to 75℃and the pressure is preferably-99 to-80 kPa. In the present invention, the concentration is preferably a program concentration including sequentially performing a first concentration and a second concentration; the temperature of the first concentration is preferably 40-50 ℃, more preferably 43-50 ℃, the pressure of the first concentration is preferably-95 kPa, and the time of the first concentration is preferably 1-3 h, more preferably 1-2 h; the temperature of the second concentration is preferably 60 to 75 ℃, more preferably 63 to 70 ℃, the pressure of the second concentration is preferably-99 to-97 kPa, more preferably-98 kPa, and the time of the second concentration is preferably 1 to 3 hours, more preferably 1 to 2 hours.
In the invention, the water-knot mother liquor and/or the waste water are preferably added in the first concentration process and the second concentration process, the water-knot mother liquor or the waste water is more preferably added in the first concentration process, and the mixed liquor of the water-knot mother liquor and the waste water is more preferably added in the second concentration process; preferably, the jellyfish solution and/or wastewater is added after the temperature reaches the temperature and pressure of the first concentration or the temperature and pressure of the second concentration. In the present invention, the content of sucralose-6-ester in the aqueous mother liquor is preferably 10 to 20g/L, more preferably 15 to 20g/L. In the invention, the wastewater comprises at least one of activated carbon washing water, inorganic salt wastewater, adsorption wastewater, waste water and slag discharging water; the jellyfish solution, the activated carbon washing water, the inorganic salt wastewater, the adsorption wastewater, the waste water and the slag discharging water are all preferably derived from the production process of the sucralose, and the jellyfish solution, the activated carbon washing water, the inorganic salt wastewater, the waste water and the slag discharging water which are well known to the person skilled in the art are adopted, specifically, the salt-free wastewater is from the water extracted by distilling the solvent recovery section ester extractant; the adsorption wastewater is from vapor condensate water generated by analysis of a trichloroethane adsorption system; the waste clean water is from water generated by a ladle baking work section; the deslagging water is water generated by a deslagging kettle of a filter pressing working section through a filter press; the activated carbon washing water is water obtained by washing activated carbon in a filter press by water from a filter press washing section; the jellied mother liquid is obtained from mother liquid generated by sugar throwing in the refining section and is sleeved with water added after the concentration drying is finished. In the invention, the volume ratio of the jellyfish solution to the wastewater is preferably 1.2-2: 1.8 to 3, more preferably 1.5 to 2:2.5 to 3. In the present invention, the mixing is preferably performed under stirring.
In the present invention, the temperature of the heat preservation is preferably 60 to 65 ℃, more preferably 61 to 64 ℃, and the heat preservation time of the heat preservation is preferably 1 to 3 hours, more preferably 2 hours.
After the concentrated dry liquid is obtained, the concentrated dry liquid is mixed with the activated carbon, the pH value is regulated to 6-9 by using ammonia water, and solid-liquid separation is carried out after decolorization treatment, so that decolorized liquid and adsorption activated carbon are respectively obtained.
The present invention is not particularly limited, and the raw materials may be uniformly mixed by a mixing method well known to those skilled in the art, such as stirring and mixing.
In the present invention, the mass of the activated carbon is preferably 0.5 to 2% of the mass of the concentrated dry liquid, and more preferably 1 to 1.5%. In the present invention, the adsorption activated carbon is preferably regenerated after washing with water and press filtration, and the method of regeneration is not particularly limited, and a method of regenerating activated carbon known to those skilled in the art may be used.
In the present invention, the concentration of the aqueous ammonia is preferably 20 to 25wt%, more preferably 21 to 24wt%.
In the present invention, the temperature of the decoloring treatment is preferably 60 to 65 ℃, more preferably 62 to 64 ℃, and the decoloring treatment time is preferably 1 to 3 hours, more preferably 1 to 2 hours.
The solid-liquid separation is not particularly limited, and the raw materials can be uniformly mixed by a solid-liquid separation method well known to those skilled in the art, specifically, for example, press filtration is preferably performed in a press filter, the pressure of the press filtration is preferably 0.03 to 0.07MPa, more preferably 0.05MPa, and the purpose of the solid-liquid separation is to remove activated carbon and inorganic salts.
After obtaining a decolorized solution, mixing the decolorized solution, an ester extractant and water phase, and cooling and crystallizing to obtain crude sugar; the aqueous phase comprises water and/or an ester-bound aqueous phase.
In the present invention, the ester extractant is preferably ethyl acetate. In the invention, the volume ratio of the decolorization liquid to the ester extractant is preferably 1:0.45 to 0.6, more preferably 1:0.5 to 0.58.
In the present invention, the volume ratio of the decolorized solution to the aqueous phase is preferably 1:0.04 to 0.13, more preferably 0.07 to 0.13. In the present invention, the aqueous phase is more preferably an ester-linked aqueous phase, and the present invention is not particularly limited, and the ester-linked aqueous phase generated in the process of preparing sucralose, which is well known to those skilled in the art, may be used, specifically, an aqueous phase obtained by layering a mother solution after press filtration in an ester-linked section.
In the invention, the initial temperature of the cooling crystallization is preferably 20 ℃, and the cooling rate of the cooling crystallization is preferably 10-20 ℃/h, more preferably 15 ℃/h; the temperature of the cooling crystallization is preferably-3 to 10 ℃, preferably 0 to 6 ℃, and the time of the cooling crystallization is preferably 4 to 6 hours, more preferably 4.5 to 5.5 hours when the temperature is reduced to the temperature of the cooling crystallization.
After the cooling crystallization, the invention further comprises the following steps: and (3) carrying out solid-liquid separation on the obtained cooling crystallization system to obtain crude sugar. The solid-liquid separation is not particularly limited, and the raw materials can be uniformly mixed by a solid-liquid separation method well known to those skilled in the art, specifically, press filtration is preferably performed in a press filter, and the pressure of the press filtration is preferably 0.03 to 0.07MPa, more preferably 0.05MPa.
In the present invention, the crude sugar preferably includes sucralose-6-ester, sucralose dichloro ester, sucralose polychloride ester, and sucralose.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples and comparative examples:
the composition of the chloridizing neutralization solution (abbreviated as chloridizing neutralization solution) of the sucralose-6-ester used is shown in table 1:
TABLE 1 composition of chloridizing neutralization solution
| Sucralose | Sucralose dichloro ester | Sucralose-6-ester | Sucralose polychloride | |
| Example 1 | 0.88g/L | 2.5g/L | 55g/L | 1.95g/L |
| Example 2 | 1.05g/L | 3.5g/L | 54.6g/L | 2.78g/L |
| Example 3 | 0.9g/L | 2.9g/L | 59.85g/L | 2.06g/L |
| Example 4 | 1.09g/L | 2.65g/L | 55.5g/L | 1.89g/L |
| Comparative example 1 | 4.09g/L | 5.65g/L | 35.5g/L | 9.89g/L |
The ester-bonded water phase is from a water phase obtained after layering mother liquor after filter pressing in an ester bonding section; the jellied mother liquor is obtained from the mother liquor generated by sugar throwing in the refining section and is sleeved with water added after the concentration and the ending; the salt-free wastewater is water extracted from the distilled solvent recovery section ester extractant; the adsorption wastewater comes from vapor condensed water generated by analysis of a trichloroethane adsorption system; the waste clear water is water generated in the ladle baking working section; the deslagging water is water generated by a deslagging kettle of a filter pressing section through a filter press; the activated carbon washing water is water obtained by washing activated carbon in the filter press by water from a filter press section.
Example 1
The chlorination neutralization solution is treated according to the process flow diagram of example 1, and the specific steps are as follows:
(1) Pre-concentrating 8200L of chloridized neutralization solution to remove trichloroethane to obtain 5300kg of pre-concentrated solution, wherein the pre-concentration temperature is 30 ℃ and the pressure is-98 kPa;
(2) Delivering the pre-concentrated solution to a concentrated drying kettle, adding 800L of intermediate water when the temperature is raised to 40 ℃ and the pressure is minus 95kPa, and continuously stirring for 2 hours to carry out DMF; when the temperature is raised to 65 ℃ and the pressure is minus 98kPa, 5000L of water is added to be stirred for 1 hour, and then the mixture is stirred for 1 hour under the condition of 60 ℃ to obtain concentrated dry liquid; wherein, the midway water is water-knot mother liquor; the ending water is water-knot mother liquor, active carbon washing liquor and slag-discharging water, and the volume ratio of the water-knot mother liquor to the wastewater in the ending water is 2:3;
(3) Conveying the concentrated dry liquid into a heat preservation kettle, adding 50kg of active carbon at 65 ℃, adding ammonia water with the concentration of 25wt% to adjust the pH value to 7, carrying out heat preservation and decoloration treatment for 2 hours, conveying into a filter press, and carrying out filter pressing under the condition of 0.5MPa to respectively obtain adsorption active carbon and 6600L decoloration liquid; the adsorption activated carbon is subjected to water washing and pressure filtration and then is sent out for regeneration, and the liquid obtained by water washing and pressure filtration is activated carbon washing liquid;
(4) Conveying the decolorized solution to an extraction kettle, adding 3000L of ethyl acetate and 300L of ester-bonded water, uniformly mixing, conveying to a concentration crystallization kettle, cooling and crystallizing for 5 hours at 8 ℃, removing the ester phase, conveying to a filter press, and carrying out filter pressing under 0.5MPa to obtain crude sugar (sugar B, dry weight 750kg, yield 60% and purity 88%).
Example 2
The chlorination neutralization solution is treated according to the process flow diagram of example 1, and the specific steps are as follows:
(1) Pre-concentrating 8200L of chloridized neutralization solution to remove trichloroethane to obtain 5300kg of pre-concentrated solution, wherein the pre-concentration temperature is 57 ℃ and the pressure is-95 kPa;
(2) Delivering the pre-concentrated solution to a concentrated drying kettle, adding 800L of intermediate water when the temperature is raised to 44 ℃ and the pressure is minus 95kPa, and continuously stirring for 3 hours to carry out DMF; when the temperature is raised to 67 ℃ and the pressure is minus 97kPa, 5000L of water is added to continue stirring for 2 hours, and then the mixture is stirred for 2 hours under the condition of 62 ℃ to obtain concentrated dry liquid; wherein, the midway water is water-knot mother liquor; the ending water is jellyfish liquid and activated carbon washing water, and the volume ratio of the jellyfish liquid to the wastewater in the ending water is 2:3;
(3) Conveying the concentrated dry liquid into a heat preservation kettle, adding 50kg of active carbon at 60 ℃, adding ammonia water with the concentration of 25wt% to adjust the pH value to 8, carrying out heat preservation and decoloration treatment for 2 hours, conveying into a filter press, and carrying out filter pressing under the condition of 0.5MPa to respectively obtain adsorption active carbon and 6600L decoloration liquid; the adsorption activated carbon is subjected to water washing and filter pressing and then is sent out for regeneration;
(4) Conveying the decolorized solution to an extraction kettle, adding 3300L of ethyl acetate and 500L of ester-bonded water, uniformly mixing, conveying to a concentration crystallization kettle, cooling and crystallizing for 4 hours at 6 ℃, removing the ester phase, conveying to a filter press, and carrying out filter pressing under the condition of 0.5MPa to obtain sugar B (dry weight 780kg, yield 61.5% and purity 88.6%).
Example 3
The chlorination neutralization solution is treated according to the process flow diagram of example 1, and the specific steps are as follows:
(1) Pre-concentrating 8200L of chloridized neutralization solution to remove trichloroethane to obtain 5300kg of pre-concentrated solution, wherein the pre-concentration temperature is 58 ℃ and the pressure is-95 kPa;
(2) Delivering the pre-concentrated solution into a concentrated drying kettle, adding 700L of intermediate water when the temperature is raised to 48 ℃ and the pressure is minus 95kPa, and continuously stirring for 3 hours to carry out DMF; adding 5000L of water after finishing stirring for 1h when the temperature is raised to 69 ℃ and the pressure is minus 99kPa, and then preserving heat and stirring for 1h at 63 ℃ to obtain concentrated dry liquid; wherein, the midway water is water-knot mother liquor; the ending water is jellyfish liquid, activated carbon washing water and slag discharging water;
(3) Conveying the concentrated dry liquid into a heat preservation kettle, adding 50kg of active carbon at 65 ℃, adding ammonia water with the concentration of 25wt% to adjust the pH value to 6, carrying out heat preservation and decoloration treatment for 2 hours, conveying into a filter press, and carrying out filter pressing under the condition of 0.5MPa to respectively obtain adsorption active carbon and 6600L decoloration liquid; the adsorption activated carbon is subjected to water washing and filter pressing and then is sent out for regeneration;
(4) And conveying the decolorized solution to an extraction kettle, adding 3500L of ethyl acetate and 800L of ester-bonded water, uniformly mixing, conveying to a concentration crystallization kettle, cooling and crystallizing for 3 hours at 2 ℃, removing the ester phase, conveying to a filter press, and carrying out filter pressing under the condition of 0.5MPa to obtain sugar B (dry weight 850kg, yield 65% and purity 92%).
Example 4
The chlorination neutralization solution is treated according to the process flow diagram of example 1, and the specific steps are as follows:
(1) Pre-concentrating 8200L of chloridized neutralization solution to remove trichloroethane to obtain 5300kg of pre-concentrated solution, wherein the pre-concentration temperature is 59 ℃ and the pressure is-95 kPa;
(2) Delivering the pre-concentrated solution into a concentrated drying kettle, adding 800L of intermediate water when the temperature is raised to 50 ℃ and the pressure is minus 95kPa, and continuously stirring for 1h to carry out DMF; when the temperature is raised to 74 ℃ and the pressure is minus 97kPa, 5000L of water is added to continue stirring for 3 hours, and then the mixture is stirred for 2 hours at 64 ℃ under the condition of heat preservation, so as to obtain concentrated dry liquid; wherein, the midway water is adsorption wastewater; the end water is slag discharging water;
(3) Conveying the concentrated dry liquid into a heat preservation kettle, adding 50kg of active carbon at 64 ℃, adding ammonia water with the concentration of 25wt% to adjust the pH value to 6, carrying out heat preservation and decoloration treatment for 3 hours, conveying into a filter press, and carrying out filter pressing under the condition of 0.5MPa to respectively obtain adsorption active carbon and 6600L decoloration liquid; the adsorption activated carbon is subjected to water washing and filter pressing and then is sent out for regeneration;
(4) Delivering the decolorized solution to an extraction kettle, adding 3800L of ethyl acetate and 600L of ester-bonded water, uniformly mixing, delivering to a concentration crystallization kettle, cooling and crystallizing for 6h at 0.3 ℃, removing the ester phase, delivering to a filter press, and carrying out filter pressing under 0.5MPa to obtain sugar B (dry weight 800kg, yield 63% and purity 90.8%).
Comparative example 1
The chlorination neutralization solution is treated according to the process flow diagram of example 1, and the specific steps are as follows:
(1) Pre-concentrating 8200L of chloridized neutralization solution to remove trichloroethane to obtain 5300kg of pre-concentrated solution, wherein the pre-concentration temperature is 68 ℃ and the pre-concentration pressure is-92 kPa;
(2) Delivering the pre-concentrated solution into a concentrated drying kettle, adding 800L of intermediate water when the temperature is raised to 50 ℃ and the pressure is minus 95kPa, and continuously stirring for 2 hours to carry out DMF; when the temperature is raised to 80 ℃ and the pressure is minus 92kPa, 5000L of water is added to be stirred for 2 hours, and then the mixture is stirred for 2 hours at 70 ℃ under the condition of heat preservation, so as to obtain concentrated dry liquid; wherein, the midway water is activated carbon washing water; the ending water is jellyfish liquid;
(3) Conveying the concentrated dry liquid into a heat preservation kettle, adding 50kg of active carbon at 68 ℃, adding ammonia water with the concentration of 25wt% to adjust the pH value to 11, carrying out heat preservation and decoloration treatment for 3 hours, conveying into a filter press, and carrying out filter pressing under the condition of 0.5MPa to respectively obtain adsorption active carbon and 6600L decoloration liquid; the adsorption activated carbon is subjected to water washing and filter pressing and then is sent out for regeneration;
(4) And (3) conveying the decolorized solution to an extraction kettle, adding 4800L of ethyl acetate and 600L of ester-bonded water, uniformly mixing, conveying to a concentration crystallization kettle, cooling and crystallizing for 2 hours at 3 ℃, removing the ester phase, conveying to a filter press, and carrying out filter pressing under the condition of 0.5MPa to obtain sugar B (dry weight 600kg, yield 55% and purity 80.6%).
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A method for treating crude sugar in a chlorination neutralization solution of sucralose-6-ester, comprising the steps of:
(1) Pre-concentrating the chloridized neutralization solution of the sucralose-6-ester to recover the trichloromethane to obtain a pre-concentrated solution;
(2) Concentrating and preserving the pre-concentrate in sequence to recover N, N-dimethylformamide to obtain concentrated dry liquid;
(3) Mixing the concentrated dry liquid with activated carbon, regulating the pH value to 6-9 by using ammonia water, and carrying out solid-liquid separation after decolorization treatment to obtain decolorized liquid and adsorption activated carbon respectively;
(4) Mixing the decolorized solution, the ester extractant and the water phase, and cooling and crystallizing to obtain crude sugar; the aqueous phase comprises water and/or an ester-bound aqueous phase.
2. The process according to claim 1, wherein in step (1), the pre-concentration is carried out at a temperature of 30 to 65 ℃ and a pressure of-99 to-90 kPa, and the volume of the pre-concentrated solution is 60 to 70% of the volume of the chlorinated neutralization solution of the sucralose-6-ester.
3. The process according to claim 1, wherein in step (2), the concentration is carried out at a temperature of 40 to 75 ℃ and a pressure of-99 to-80 kPa;
the temperature of the heat preservation is 60-65 ℃ and the time is 1-3 h.
4. A treatment method according to claim 1 or 3, wherein the concentration process is performed by adding a water-knot mother liquor or a mixed liquor of the water-knot mother liquor and wastewater;
the content of the sucralose-6-ester in the water knot mother liquor is 10-20 g/L;
the wastewater comprises at least one of activated carbon washing water, inorganic salt wastewater, adsorption wastewater, waste clear water and slag discharging water;
the volume ratio of the jellyfish liquid to the wastewater is 1.2-2: 1.8 to 3.
5. The method according to claim 1, wherein in the step (3), the mass of the activated carbon is 0.5 to 2% of the mass of the concentrated dry liquid.
6. The method according to claim 1, wherein in the step (3), the concentration of the aqueous ammonia is 20 to 25wt%.
7. The method according to claim 1, 6 or 7, wherein in the step (3), the decoloring treatment is performed at a temperature of 60 to 65 ℃ for a time of 1 to 3 hours.
8. The process of claim 1, wherein in step (4), the volume ratio of the decolorized solution to the ester extractant is 1:0.45 to 0.6;
the volume ratio of the decolorized solution to the water phase is 1:0.04 to 0.13.
9. The process according to claim 1 or 9, wherein in step (4), the temperature of the reduced temperature crystallization is-3 to 10 ℃ for 4 to 6 hours.
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| 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 |
| CN109574792A (en) * | 2018-12-14 | 2019-04-05 | 安徽金禾实业股份有限公司 | A kind of Sucralose DMF wastewater of rectification recycling and reusing method |
| 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 |
| CN114106065A (en) * | 2021-12-20 | 2022-03-01 | 安徽金禾实业股份有限公司 | Method for directly preparing sucralose by sucralose chlorination liquid |
| CN115672222A (en) * | 2022-11-17 | 2023-02-03 | 安徽金禾实业股份有限公司 | Device and method for pretreatment of chlorination neutralization solution and recovery of solvent in sucralose production |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN109574792A (en) * | 2018-12-14 | 2019-04-05 | 安徽金禾实业股份有限公司 | A kind of Sucralose DMF wastewater of rectification recycling and reusing method |
| 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 |
| CN114106065A (en) * | 2021-12-20 | 2022-03-01 | 安徽金禾实业股份有限公司 | Method for directly preparing sucralose by sucralose chlorination liquid |
| CN115672222A (en) * | 2022-11-17 | 2023-02-03 | 安徽金禾实业股份有限公司 | Device and method for pretreatment of chlorination neutralization solution and recovery of solvent in sucralose production |
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