CN116425811A - Sucralose solution crystallization process - Google Patents
Sucralose solution crystallization process Download PDFInfo
- Publication number
- CN116425811A CN116425811A CN202310360649.3A CN202310360649A CN116425811A CN 116425811 A CN116425811 A CN 116425811A CN 202310360649 A CN202310360649 A CN 202310360649A CN 116425811 A CN116425811 A CN 116425811A
- Authority
- CN
- China
- Prior art keywords
- sucralose
- organic solvent
- solvent
- crystallization
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004376 Sucralose Substances 0.000 title claims abstract description 137
- 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 title claims abstract description 129
- 235000019408 sucralose Nutrition 0.000 title claims abstract description 129
- 238000002425 crystallisation Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000008025 crystallization Effects 0.000 title claims abstract description 31
- 239000003960 organic solvent Substances 0.000 claims abstract description 57
- 239000013078 crystal Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 239000005720 sucrose Substances 0.000 claims abstract description 14
- 229930006000 Sucrose Natural products 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 9
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 25
- 238000000605 extraction Methods 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 10
- 239000005642 Oleic acid Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 7
- 229940011051 isopropyl acetate Drugs 0.000 claims description 7
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 7
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 6
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 6
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 6
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 229940090181 propyl acetate Drugs 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 5
- 229940072049 amyl acetate Drugs 0.000 claims description 5
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 5
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 claims description 4
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 claims description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 4
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 3
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 3
- QQQCWVDPMPFUGF-ZDUSSCGKSA-N alpinetin Chemical compound C1([C@H]2OC=3C=C(O)C=C(C=3C(=O)C2)OC)=CC=CC=C1 QQQCWVDPMPFUGF-ZDUSSCGKSA-N 0.000 claims description 3
- 229940043232 butyl acetate Drugs 0.000 claims description 3
- 229940093499 ethyl acetate Drugs 0.000 claims description 3
- 229940117955 isoamyl acetate Drugs 0.000 claims description 3
- 229960004488 linolenic acid Drugs 0.000 claims description 3
- 235000021313 oleic acid Nutrition 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- TWSRVQVEYJNFKQ-UHFFFAOYSA-N pentyl propanoate Chemical compound CCCCCOC(=O)CC TWSRVQVEYJNFKQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 20
- 239000007788 liquid Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000000746 purification Methods 0.000 abstract description 6
- 238000005185 salting out Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 4
- 239000012043 crude product Substances 0.000 abstract description 4
- 239000012071 phase Substances 0.000 description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 7
- 238000004042 decolorization Methods 0.000 description 7
- 238000000105 evaporative light scattering detection Methods 0.000 description 7
- 238000006136 alcoholysis reaction Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000000397 acetylating effect Effects 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012296 anti-solvent Substances 0.000 description 2
- 239000008122 artificial sweetener Substances 0.000 description 2
- 235000021311 artificial sweeteners Nutrition 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- -1 sucrose acyl compound Chemical class 0.000 description 2
- 150000003445 sucroses Chemical class 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- BAQAVOSOZGMPRM-UGDNZRGBSA-N (2R,3R,4R,5S,6R)-2-[(2R,3S,4S,5S)-2,5-bis(chloromethyl)-3,4-dihydroxyoxolan-2-yl]oxy-5-chloro-6-(hydroxymethyl)oxane-3,4-diol 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-UGDNZRGBSA-N 0.000 description 1
- UQXZSKHOYOHVIH-UGDNZRGBSA-N (2R,3R,4S,5S,6R)-2-[(2R,3S,4S,5S)-2,5-bis(chloromethyl)-3,4-dihydroxyoxolan-2-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@]1(CCl)[C@@H](O)[C@H](O)[C@@H](CCl)O1 UQXZSKHOYOHVIH-UGDNZRGBSA-N 0.000 description 1
- MLQSSVPAOPJIFW-UYFOZJQFSA-N (3s,4s,5s)-1,6-dichloro-3,4,5-trihydroxyhexan-2-one Chemical compound ClC[C@@H](O)[C@@H](O)[C@H](O)C(=O)CCl MLQSSVPAOPJIFW-UYFOZJQFSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002635 aromatic organic solvent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229960003328 benzoyl peroxide Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- QQVDYSUDFZZPSU-UHFFFAOYSA-M chloromethylidene(dimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)=CCl QQVDYSUDFZZPSU-UHFFFAOYSA-M 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- OYJXTOVLKZDGFK-UHFFFAOYSA-N ethanol;2-propan-2-yloxypropane Chemical compound CCO.CC(C)OC(C)C OYJXTOVLKZDGFK-UHFFFAOYSA-N 0.000 description 1
- ZDQQJELPDUQGLA-UHFFFAOYSA-N ethanol;3-methylbutanoic acid Chemical compound CCO.CC(C)CC(O)=O ZDQQJELPDUQGLA-UHFFFAOYSA-N 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
Abstract
The invention provides a sucralose solution crystallization process. And (3) carrying out high-concentration sodium hydroxide catalytic treatment on the sucrose acylation-chlorination reaction liquid to obtain a sucralose mixed liquid, removing residues and desolventizing the mixed liquid to obtain a sucralose crude product aqueous solution, and extracting the aqueous solution step by using a first organic solvent and a second organic solvent to enrich a large amount of sucralose in the second organic solvent phase, and decoloring and concentrating to obtain a sucralose crude product. And adding a third and a fourth organic solvents step by step to completely dissolve the organic solvents, finally forming a solvent-anti-solvent crystallization system, adding a small amount of seed crystals into the solvent-anti-solvent crystallization system, efficiently obtaining sucralose crystals at room temperature and constant temperature, recrystallizing with one-step pure water through one-step solvent-anti-solvent crystallization, and drying to obtain qualified sucralose products (purity more than 98%). The process greatly simplifies the production steps of the sucralose, shortens the three-step reaction of the traditional process to two steps, simplifies the purification steps of the sucralose, and has better industrial value.
Description
Technical Field
The invention relates to the field of sucralose crystallization separation, in particular to a method for efficiently purifying sucralose based on a solution crystallization technology, belonging to the technical field of sucralose production.
Background
Sucralose (Sucralose), commonly known as Sucralose, is one of the halogenated sucrose derivatives, and Sucralose is an artificial sweetener using sucrose as a raw material, and the sweetness of Sucralose is 400-800 times that of sucrose. Sucralose has been widely used in more than 400 foods. The low calorie beverage is the largest market for artificial sweeteners, and the low calorie beverage will be the key point of market promotion in the future, which will undoubtedly greatly increase the market demand for sucralose. In recent years, the global sucralose productivity and market demand steadily increase, and the sucralose has become the variety with the fastest demand speed increase in the sweet ingredient market, and the market development trend is good.
The existing industrial synthesis route of the sucralose mainly adopts a single-group protection method, and the qualified sucralose product can be obtained only by 3 chemical reaction processes such as acylation, chlorination, alcoholysis and the like and more than 20 separation processes, so that the process flow is tedious and lengthy, the energy consumption of production is high, the efficiency is low, and the solvent consumption is large, thereby severely limiting the industrial production scale of the sucralose and the development of the sucralose industry. The 3 rd step of the base catalyzed alcoholysis reaction in the sucralose production process is a similar and repeated operation as the 2 nd step of the chlor-alkali quenching neutralization reaction, and the root cause is that the separation efficiency of the intermediate sucralose-6-acetate is far greater than that of sucralose. Therefore, research on efficient purification technology of sucralose has important significance for production of sucralose.
At present, many patent reports on purifying sucralose are reported, for example, US4980463, an alcoholysis reaction solution is concentrated to prepare a crude sucralose aqueous solution, methyl benzoate is adopted for one-time extraction, water is used for back extraction, decolorization and concentration are carried out, and finally pure sucralose is obtained by crystallization. US5498709 uses ethyl acetate solvent to extract aqueous solution of sucralose, then uses water to wash to remove residual N, N-dimethylformamide, and finally concentrates and crystallizes to obtain sucralose. US7049435 uses two non-aromatic organic solvents to extract aqueous solutions of sucralose respectively, so that impurities remain in the organic solvent and the aqueous phase, and high-purity sucralose is obtained by concentrating and crystallizing from the other organic solvent phase. CN1330659 is prepared by purifying sucralose stock solution by adopting non-crystallization methods such as liquid-liquid extraction, extraction precipitation, chromatography or distillation with ethyl acetate and water, and continuously crystallizing for three or more times and recycling mother solution to obtain pure sucralose. And slowly cooling and crystallizing the US20090208747 in a mixed alcohol solvent to obtain sucralose crystals. CN100567319 uses a mixed solvent of water and alcohol or a mixed solvent of water and ethyl acetate to crystallize sucralose. CN100591684 uses the difference between the polarity and boiling point of the mixed solvent, concentrates the solvent with stronger polarity/lower boiling point, and crystallizes to obtain the sucralose. CN112543760 is obtained by extracting nonpolar impurities in aqueous solution of sucralose by ethyl acetate or isopropyl acetate, concentrating and recrystallizing the aqueous solution. However, all of the above reports use a sucralose feed solution obtained by an alcoholysis process as a purification starting material, in which impurities gradually accumulated during sucrose acylation and chlorination have been purified, and the whole process requires a sucralose-6-acetate purification and a one-step alcoholysis reaction, and the process flow is very complicated.
Disclosure of Invention
The invention aims to solve the existing technical bottleneck, and provides a process for producing the sucralose by using a crystallization mechanism, which solves the problems of difficult crystallization, low crystallization speed and the like of a complex sucralose-impurity system, realizes the efficient crystallization and separation of the sucralose, shortens the reaction steps, simplifies the purification process and reduces the production cost of the sucralose.
In order to achieve the above object, the technical scheme of the present invention is as follows:
a sucralose solution crystallization production process comprises the following steps:
filtering the mixed solution of the sucralose, removing residues, concentrating, removing the solvent, preparing an aqueous solution of a crude sucralose product by using pure water, further extracting the aqueous solution step by using a first organic solvent and a second organic solvent, enriching a large amount of the sucralose in the second organic solvent phase, decoloring, and concentrating to obtain the crude sucralose product.
Step two, adding a third and a fourth organic solvents step by step to completely dissolve the crude sucralose product, finally forming a solvent-anti-solvent sucralose solution crystallization system, adding a small amount of seed crystals into the solvent-anti-solvent crystallization system, stirring to form a solvent-anti-solvent system, obtaining sucralose crystals at room temperature and constant temperature with high efficiency, and performing solvent-anti-solvent crystallization again to obtain sucralose solid powder. Dissolving the compound with pure water, cooling, recrystallizing, and drying to obtain qualified sucralose product.
Further, the mixed solution of the sucralose in the first step is prepared by slowly dropwise adding 40-80 wt% sodium hydroxide aqueous solution to pH >10.5 at-10-40 ℃ to catalyze for 1-5 h, and quenching with 36wt% hydrochloric acid to obtain a mixed solution of the sucralose, wherein the mixed solution comprises tens of main chlorinated sucrose byproducts such as 4,1',6' -sucralose, 4,6' -sucralose, 1',6' -sucralose, 6,4,6' -sucralose, 6,1',6' -sucralose, 2,4,1',6' -tetrachlorosucrose, 6,4,1',6' -tetrachlorosucrose and organic solvents such as carbon residue, hydrochloride, tar, 1, 2-trichloroethane, N ' -dimethylformamide, and the actual content of the 4,1',6' -trichlorosucrose is 1-10 wt%.
The sucrose acylation-chlorination reaction liquid is a liquid obtained by selectively acetylating a sucrose 6-hydroxyl group, but directly carrying out selective chlorination on a sucrose-6-acetate without purifying, wherein the sucrose 6-hydroxyl group selective acetylating method is a dibutyl tin oxide method, and the 4,1',6' -hydroxyl group selective chlorinating method is a Vilsmeier reagent method, and the specific steps comprise: (1) Adding a catalyst 1, 3-bis (acetoxyl) -1, 3-tetrabutyl distannoxane (DSDA) into an N, N-dimethylformamide solution of sucrose, carrying out reduced pressure distillation at 80-90 ℃ to continuously take out water generated by the reaction until any liquid cannot be evaporated, adding a certain amount of N, N' -dimethylformamide, cooling to-5 ℃, dropwise adding acetic anhydride, stirring for 3-6 h, and then adding deionized quenching. Finally, cyclohexane is used for extraction and recovery of DSDA in the reaction liquid, acetic acid and water are removed through reduced pressure distillation at the temperature of 60-80 ℃, and N, N' -dimethylformamide is added to prepare sucrose acyl compound liquid. (2) Dropwise adding a sucrose acyl compound into a mixed solution of 1, 2-trichloroethane and thionyl chloride at the temperature of-5 ℃, heating to 20-35 ℃, stirring for 0.5-1 h, heating to 70-85 ℃ at 1-2 ℃/min for reacting for 1-1.5 h, heating to 90-100 ℃ at 0.5-1 ℃/min for reacting for 1-1.5 h, and heating to 105-115 ℃ at 0.1-0.3 ℃/min for reflux reacting for 1-2 h; to obtain sucrose acylation-chlorination reaction liquid.
The first step of filtering to remove slag refers to removing solid particles such as carbon slag, salt and the like by suction filtration;
the first step of concentrating and desolventizing refers to removing more than 90wt% of 1, 2-trichloroethane, N' -dimethylformamide and other organic solvents by reduced pressure distillation at 50-90 ℃;
preferably, the first organic solvent in the first step is at least one of butyl acetate, amyl acetate, isoamyl acetate, butyl propionate and amyl propionate.
Preferably, the mass ratio of the first organic solvent to the aqueous solution in the first step is 0.2:1-2:1.
Preferably, the second organic solvent in the first step is at least one of ethyl acetate, propyl acetate, isopropyl acetate and ethyl propionate.
Preferably, the mass ratio of the second organic solvent to the aqueous solution in the first step is 0.2:1-2:1.
The first step of decoloring and concentrating refers to adding 1/5-1/20 times of active carbon of a second organic solvent phase for decoloring, filtering the active carbon, and removing the second organic solvent by reduced pressure distillation for 30-240 min at the temperature of 30-70 ℃ under the pressure of 0.07-0.1 MPa;
preferably, the third organic solvent in the second step is at least one of methanol and ethanol.
Preferably, the mass ratio of the third organic solvent to the sucralose crude product in the second step is 4:1-20:1.
Preferably, the fourth organic solvent in the second step is at least one of oleic acid, linoleic acid, alpha-linolenic acid, isovaleric acid, n-caproic acid, n-heptanoic acid, n-decanoic acid, n-propyl ether and isopropyl ether.
Preferably, the mass ratio of the fourth organic solvent to the third organic solvent in the second step is 1:1-20:1.
Preferably, the mass ratio of the sucralose seed crystal and the third organic solvent in the second step is 0.0008:1-0.05:1.
Preferably, the stirring crystallization time in the second step is 3-24 h.
Preferably, the crystallization temperature in the second step is any constant temperature within a range of 10-40 ℃.
Preferably, the mass ratio of the sucralose solid to the pure water in the second step is 4:1-20:1.
Preferably, the pure water recrystallization temperature in the second step is 50-60 ℃ and is reduced to 0-10 ℃.
Preferably, the drying temperature in the second step is 40-60 ℃, the pressure is-0.1-0.04 MPa, and the drying time is 12-24 hours.
It should be noted that the actual content of the sucralose in the sucralose mixture liquid in the first step is 1-10wt%, and the HPLC-ELSD shows the purity of 30-40%. The actual purity of the qualified sucralose product described in the second step exceeds 98% and the HPLC-ELSD shows a purity of greater than 99.4%.
Compared with the prior art, the invention has the advantages and outstanding effects that:
(1) In the process of purifying the sucralose, the method has the characteristics of high crystallization speed, higher separation selectivity, high yield and the like, and meanwhile, the solvent-antisolvent crystallization is carried out at room temperature and constant temperature (the error is not more than +/-1 ℃), so that the energy consumption in the crystallization process is greatly reduced, and the method is mild in condition, convenient to operate and suitable for industrial application.
(2) The method combines alkali chloride neutralization and alkali catalytic alcoholysis in the process of producing the sucralose into a whole, greatly simplifies the steps of producing the sucralose, directly shortens the three-step reaction of the traditional process into two-step reaction, shortens the purification process in the production process, and has excellent industrial value.
Drawings
FIG. 1 is a route diagram of the sucralose production process of the present invention;
FIG. 2 is a HPLC-ELSD chromatogram before and after the elution crystallization of sucralose of example 1, a-sucralose (1 ',6' -dichloro-1 ',6' -dideoxysucrose, 1, 6-dichloro-1, 6-dideoxy-D-fructose); b-sucralose; c-sucralose (1 ',6' -trichloro-1 ',6' -trideoxy-sucrose); d-sucralose-6-acetate;
FIG. 3 is a FT-IR chart of example 1 before and after a sucralose solution crystallization;
FIG. 4 is an XRD pattern of example 1 before and after the solution crystallization of sucralose;
FIG. 5 is an SEM image after the solution crystallization of sucralose of example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples.
A process for the solution crystallization of sucralose, comprising the steps of:
1) Concentrating the aqueous solution of the crude sucralose product into an organic phase through fractional extraction, decoloring and concentrating to obtain the crude sucralose product; the step-by-step extraction uses a first organic solvent and a second organic solvent;
2) Step-by-step adding a third organic solvent which is 4-20 times the mass of the crude sucralose product and a fourth organic solvent which is 1-20 times the mass of the third organic solvent, so that the crude sucralose product is completely dissolved; adding a small amount of seed crystal and stirring to obtain sucralose crystals;
3) Adding a third organic solvent which is 4-20 times of the mass of the sucralose crystals and a fourth organic solvent which is 1-20 times of the mass of the third organic solvent step by step, so that the sucralose crystals are completely dissolved; adding a small amount of seed crystal into the mixture and stirring the mixture to obtain sucralose solid powder;
4) Dissolving the sucralose solid powder in pure water with the mass of 4-20 times, cooling, recrystallizing, and drying the crystallized product to obtain the sucralose product.
Further, the aqueous solution of the crude sucralose is a mixed solution of sucralose obtained by carrying out low-temperature catalytic treatment on a sucrose acylation-chlorination reaction solution by high-concentration sodium hydroxide and quenching by hydrochloric acid, and is a solution which is dissolved by pure water after being subjected to solid particle removal treatment, reduced pressure distillation to remove more than 90% of organic solvent treatment.
Further, the step extraction comprises extraction with a first organic solvent and a second organic solvent, the first organic solvent comprising butyl acetate, amyl acetate, isoamyl acetate, butyl propionate, or amyl propionate; the second organic solvent comprises ethyl acetate, propyl acetate, isopropyl acetate or ethyl propionate.
Further, "decolorization and concentration" means that activated carbon is used for decolorization, the activated carbon is removed by filtration, and the organic solvent is removed by reduced pressure distillation for 30-240 min at the temperature of 30-70 ℃ under the pressure of 0.07-0.1 MPa.
Further, the third organic solvent comprises methanol or ethanol; the fourth organic solvent comprises oleic acid, linoleic acid, alpha-linolenic acid, isovaleric acid, n-caproic acid, n-heptanoic acid, n-decanoic acid, n-propyl ether or isopropyl ether.
Further, the temperature reduction recrystallization is to reduce the temperature from 50-60 ℃ to 0-10 ℃.
Example 1
An aqueous solution of 7.5wt% sucralose crude product, 10 g, was added to 10 g butyl acetate for extraction, and the aqueous phase and butyl acetate phase were separated. Then adding 10 g ethyl acetate into the water phase for extraction, separating the water phase and the ethyl acetate phase, adding 2g of active carbon into the organic phase for decolorization, filtering, and completely evaporating the ethyl acetate at 50 ℃ and 0.1 MPa to obtain a crude sucralose product. 3 g methanol is used for dissolving the crude sucralose, 3 g oleic acid and 0.003 g high-purity sucralose solid are added after complete dissolution, stirring is carried out at 30 ℃ and 1000 r/min, white crystals are continuously separated out from the system, stirring is stopped after 12 h, all solid and liquid are taken out, centrifugal separation is carried out, and the obtained solid is subjected to repeated 'methanol-oleic acid' crystallization experiment. Finally, dissolving the obtained solid in pure water at 60 ℃ and removing a small amount of suspended oleic acid, slowly cooling to 10 ℃ to obtain sucralose crystals, drying the crystals at 50 ℃ in vacuum until the crystals are complete, and analyzing the crystals by weighing and HPLC-ELSD, wherein the relative content of the sucralose is 99.25wt%.
Example 2
An aqueous solution 10 g of a crude sucralose product with a content of 7.5wt% was added to 12 g butyl acetate for extraction, and the aqueous phase and the butyl acetate phase were separated. Then adding 12 g ethyl acetate into the water phase for extraction, separating the water phase and the ethyl acetate phase, adding 2g of active carbon into the organic phase for decolorization, filtering, and completely evaporating the ethyl acetate at 50 ℃ and 0.1 MPa to obtain a crude sucralose product. After the crude sucralose is completely dissolved, 2.5 g methanol is used for dissolving, 2.5 g oleic acid and 0.0025 g high-purity sucralose solid are added and stirred at 30 ℃ and 1000 r/min, white crystals are continuously separated out from the system, stirring is stopped after 12 h, all the solid and liquid are taken out, centrifugal separation is carried out, and the obtained solid is subjected to repeated 'methanol-oleic acid' crystallization experiments. Finally, dissolving the obtained solid in pure water at 60 ℃ and removing a small amount of suspended oleic acid, slowly cooling to 10 ℃ to obtain sucralose crystals, drying the crystals at 50 ℃ in vacuum until the crystals are completely dried, and analyzing the crystals by weighing and HPLC-ELSD, wherein the relative content of the sucralose is 99.51wt%.
Example 3
A crude aqueous solution of sucralose, 10 g, containing 7.5 wt.% of the crude sucralose, was extracted by adding butyl propionate 10 g, and the aqueous phase and the butyl propionate phase were separated. And adding 10 g of propyl acetate into the aqueous phase for extraction, separating the aqueous phase and the propyl acetate phase, adding 2g of active carbon into the organic phase for decolorization, filtering, and completely evaporating the propyl acetate at 50 ℃ and 0.1 MPa to obtain a crude sucralose product. After the crude sucralose is completely dissolved, 3 g isopropyl ether and 0.003 g high-purity sucralose solid are added, and stirring is carried out at 30 ℃ and 1000 r/min, white crystals are continuously separated out from the system, after 12 h, stirring is stopped, all the solid and liquid are taken out, centrifugal separation is carried out, and the obtained solid is subjected to repeated ethanol-isopropyl ether crystallization experiment once. Finally, the obtained solid is dissolved in pure water at 60 ℃, the temperature is slowly reduced to 10 ℃ to obtain sucralose crystals, the crystals are dried to be complete in vacuum at 50 ℃, and the relative content of the sucralose is 99.06wt% through weighing and HPLC-ELSD analysis.
Example 4
An aqueous solution 10 g of a crude sucralose product with a content of 7.5wt% was added to 12 g amyl acetate for extraction, and the aqueous phase and amyl acetate phase were separated. Adding 12 g isopropyl acetate into the water phase for extraction, separating the water phase and the isopropyl acetate phase, adding 2g active carbon into the organic phase for decolorization, filtering, and completely evaporating the isopropyl acetate at 50 ℃ and 0.1 MPa to obtain a crude sucralose product. Dissolving the crude sucralose product with 2.5 g ethanol, adding 2.5 g isovaleric acid and 0.0025 g high-purity sucralose solid after complete dissolution, stirring at 30 ℃ and 1000 r/min, continuously precipitating white crystals in the system, stopping stirring after 12 h, taking out all the solid and liquid, centrifuging, and repeating the crystallization experiment of ethanol-isovaleric acid for one time on the obtained solid. Finally, the obtained solid is dissolved in pure water at 60 ℃, the temperature is slowly reduced to 10 ℃ to obtain sucralose crystals, the crystals are dried to be complete in vacuum at 50 ℃, and the relative content of the sucralose is 99.35wt% through weighing and HPLC-ELSD analysis.
The foregoing detailed description of the process for producing sucralose, with reference to the examples, is illustrative and not limiting, and several examples may be enumerated in accordance with the defined scope, as such, without departing from the general inventive concept, and therefore, should be considered as falling within the scope of the present invention.
Claims (7)
1. A process for the solution crystallization of sucralose, comprising the steps of:
1) Concentrating the aqueous solution of the crude sucralose product into an organic phase through fractional extraction, decoloring and concentrating to obtain the crude sucralose product; the step-by-step extraction uses a first organic solvent and a second organic solvent;
2) Step-by-step adding a third organic solvent which is 4-20 times the mass of the crude sucralose product and a fourth organic solvent which is 1-20 times the mass of the third organic solvent, so that the crude sucralose product is completely dissolved; adding a small amount of seed crystal and stirring to obtain sucralose crystals;
3) Adding a third organic solvent which is 4-20 times of the mass of the sucralose crystals and a fourth organic solvent which is 1-20 times of the mass of the third organic solvent step by step, so that the sucralose crystals are completely dissolved; adding a small amount of seed crystal into the mixture and stirring the mixture to obtain sucralose solid powder;
4) Dissolving the sucralose solid powder in pure water with the mass of 4-20 times, cooling, recrystallizing, and drying the crystallized product to obtain the sucralose product.
2. The process for the solution crystallization of sucralose according to claim 1, wherein the aqueous solution of the crude sucralose is a solution obtained by subjecting a sucrose acylation-chlorination reaction solution to a low-temperature catalytic treatment with high-concentration sodium hydroxide and quenching with hydrochloric acid, and dissolving the solution in pure water after removing solid particles, removing more than 90% of the organic solvent by distillation under reduced pressure.
3. A sucralose solution crystallization process according to claim 1, wherein the step-wise extraction comprises extraction with a first organic solvent and a second organic solvent, the first organic solvent comprising butyl acetate, amyl acetate, isoamyl acetate, butyl propionate, or amyl propionate; the second organic solvent comprises ethyl acetate, propyl acetate, isopropyl acetate or ethyl propionate.
4. The process for the solution crystallization of sucralose according to claim 1, wherein the step of decoloring and concentrating is to decolor with activated carbon, filter and remove the activated carbon, and decompress and distill for 30-240 min at 30-70 ℃ under 0.07-0.1 MPa to remove the organic solvent.
5. A sucralose solution crystallization process according to claim 1, wherein the third organic solvent comprises methanol or ethanol; the fourth organic solvent comprises oleic acid, linoleic acid, alpha-linolenic acid, isovaleric acid, n-caproic acid, n-heptanoic acid, n-decanoic acid, n-propyl ether or isopropyl ether.
6. The process according to claim 1, wherein the crystallization temperature in steps 2) and 3) is any constant temperature within the range of 10-40 ℃ with an error of not more than ±1 ℃.
7. The process of claim 1, wherein the cooling recrystallization is from 50-60 ℃ to 0-10 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310360649.3A CN116425811A (en) | 2023-04-06 | 2023-04-06 | Sucralose solution crystallization process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310360649.3A CN116425811A (en) | 2023-04-06 | 2023-04-06 | Sucralose solution crystallization process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116425811A true CN116425811A (en) | 2023-07-14 |
Family
ID=87093846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310360649.3A Pending CN116425811A (en) | 2023-04-06 | 2023-04-06 | Sucralose solution crystallization process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116425811A (en) |
-
2023
- 2023-04-06 CN CN202310360649.3A patent/CN116425811A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101245085B (en) | Technique for synthesizing and purifying sucrose trichloride | |
| CN109627269B (en) | Method for extracting N-acetylneuraminic acid | |
| CN111087296A (en) | Method for extracting shikimic acid and shikimic acid extract | |
| EP4215538A1 (en) | Method for purifying sucralose | |
| CN110734467A (en) | method for extracting and purifying spinosad from fermentation liquor | |
| CN109553645B (en) | Method for extracting low-content erythromycin A in fermentation solution | |
| CN116425811A (en) | Sucralose solution crystallization process | |
| CN111187328B (en) | Method for preparing mogrol | |
| CN116284171B (en) | Purification method of 4,1',6' -trichlorosucrose-6-acetate | |
| CN114014897A (en) | Purification and crystallization method of sucralose | |
| CN112250564B (en) | Method for extracting shikimic acid from fermentation broth | |
| CN113150047A (en) | Method for separating and extracting sucralose-6-acetate | |
| CN116217635B (en) | Deacidifying and purifying method for sucrose-6-acetate | |
| CN111777653A (en) | Preparation method of pure natural high-content neohesperidin | |
| CN114437146B (en) | Production process of sucralose-6-acetate | |
| CN113173959B (en) | Method for removing impurities in system for enzymatically synthesizing sucrose-6-acetate | |
| CN109593107A (en) | A kind of method of purification of cane sugar-6-acetic ester | |
| CN110950918A (en) | Method for recovering erythromycin thiocyanate from erythromycin thiocyanate secondary crystallization mother liquor | |
| CN114478682B (en) | Refining method of dexamethasone epoxy hydrolysate | |
| CN113698289B (en) | Method for preparing shikimic acid from ginkgo leaf extraction waste liquid | |
| CN112457242B (en) | Preparation method of lacidipine impurity B | |
| JP3831476B2 (en) | Purification method of xylose | |
| JPS628118B2 (en) | ||
| WO2024082156A1 (en) | Method for preparing sucralose crude product by using alcohol-water alkaline hydrolysis system | |
| CN117186163A (en) | Sucralose-6-acetate purification process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |