CN108026037B - 生产牛磺酸的循环方法 - Google Patents
生产牛磺酸的循环方法 Download PDFInfo
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- CN108026037B CN108026037B CN201780001136.6A CN201780001136A CN108026037B CN 108026037 B CN108026037 B CN 108026037B CN 201780001136 A CN201780001136 A CN 201780001136A CN 108026037 B CN108026037 B CN 108026037B
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- alkali metal
- taurine
- alkali
- isethionate
- sodium
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- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229960003080 taurine Drugs 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 51
- LLOHIFXFHGMBNO-UHFFFAOYSA-N azane;2-hydroxyethanesulfonic acid Chemical compound [NH4+].OCCS([O-])(=O)=O LLOHIFXFHGMBNO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000007098 aminolysis reaction Methods 0.000 claims abstract description 9
- 229940104261 taurate Drugs 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 239000003513 alkali Substances 0.000 claims description 23
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- -1 alkali metal isethionate Chemical class 0.000 abstract description 27
- 238000005915 ammonolysis reaction Methods 0.000 abstract description 20
- 239000006227 byproduct Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 abstract description 2
- 150000004679 hydroxides Chemical class 0.000 abstract description 2
- 235000021317 phosphate Nutrition 0.000 abstract description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract description 2
- 230000001172 regenerating effect Effects 0.000 abstract description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 abstract description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000243 solution Substances 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 11
- 229940104256 sodium taurate Drugs 0.000 description 11
- GWLWWNLFFNJPDP-UHFFFAOYSA-M sodium;2-aminoethanesulfonate Chemical compound [Na+].NCCS([O-])(=O)=O GWLWWNLFFNJPDP-UHFFFAOYSA-M 0.000 description 11
- LADXKQRVAFSPTR-UHFFFAOYSA-M sodium;2-hydroxyethanesulfonate Chemical compound [Na+].OCCS([O-])(=O)=O LADXKQRVAFSPTR-UHFFFAOYSA-M 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229940045998 sodium isethionate Drugs 0.000 description 8
- 239000012452 mother liquor Substances 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 6
- 229940045996 isethionic acid Drugs 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- QEOWFDYSNYCPRK-UHFFFAOYSA-N OCC[Na] Chemical compound OCC[Na] QEOWFDYSNYCPRK-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- KRURGYOKPVLRHQ-UHFFFAOYSA-L trithionate(2-) Chemical compound [O-]S(=O)(=O)SS([O-])(=O)=O KRURGYOKPVLRHQ-UHFFFAOYSA-L 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- LSVVNVHHHMEPJZ-UHFFFAOYSA-L [Na+].[Na+].[O-]S(=O)(=O)SS([O-])(=O)=O Chemical compound [Na+].[Na+].[O-]S(=O)(=O)SS([O-])(=O)=O LSVVNVHHHMEPJZ-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000013566 allergen Substances 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M bisulphate group Chemical class S([O-])(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BBLSYMNDKUHQAG-UHFFFAOYSA-L dilithium;sulfite Chemical compound [Li+].[Li+].[O-]S([O-])=O BBLSYMNDKUHQAG-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000020774 essential nutrients Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种从羟乙基磺酸铵生产牛磺酸的方法。将羟乙基磺酸碱金属盐在二牛磺酸碱金属盐,三牛磺酸碱金属盐,或其混合物的存在下氨解,以抑制副产物的形成,并将氨解反应的副产物连续转化为牛磺酸碱金属盐。牛磺酸碱金属盐与羟乙基磺酸铵反应得到牛磺酸,再生羟乙基磺酸碱金属盐。产率提高到从90%到接近定量。氨解反应由氢氧化物,硫酸盐,亚硫酸盐,磷酸盐或碳酸盐的碱金属盐催化。
Description
本申请要求2016年9月16日提交的第15/268071号美国临时专利申请的优先权,其通过引用并入本文中。
技术领域
本发明公开一个从羟乙基磺酸铵生产牛磺酸的循环方法,整体生产收率高(即大于90%到定量)。其特征是将羟乙基磺酸碱金属盐在二牛磺酸碱金属盐和三牛磺盐碱金属盐的混合物存在下进行氨解反应,再和羟乙基磺酸铵反应。
背景技术
牛磺酸,别名2-氨基乙磺酸,是一种在许多动物组织中存在的氨基磺酸。由于其本身具有一定的药理效果,如解毒效果,缓解疲劳效果,滋养补益效果等,牛磺酸是一种极其有用的化合物。因此牛磺酸对于人和动物而言是一种必需的营养成分,有着广泛的应用。
目前每年有超过50,000吨的牛磺酸,由环氧乙烷和一乙醇胺这两种石油衍生化合物制备而来。目前大部分的牛磺酸是由环氧乙烷通过三步制备而来的:(1)环氧乙烷和亚硫酸氢钠的加成反应得到羟乙基磺酸钠;(2)氨解羟乙基磺酸钠得到牛磺酸钠;(3)使用盐酸,最好是硫酸中和反应,得到牛磺酸和无机盐。
尽管由环氧乙烷合成牛磺酸的方法已经建立得很完善,并被广泛地用于合成牛磺酸商业产品,但是这个方法的总产率不高,只有不超过80%。而且这个方法会产生大量的废料,不易处理。
由环氧乙烷合成牛磺酸方法的第一步是环氧乙烷和亚硫酸氢钠的加成反应,在特定的条件下,见美国专利号2,820,818,能高产率地得到羟乙基磺酸钠,实际中可以达到定量的产率。
因此,由环氧乙烷生产牛磺酸的方法的问题出现在羟乙基磺酸钠的氨解过程和牛磺酸同硫酸钠的分离过程中。
美国专利号1,932,907发现,当羟乙基磺酸钠氨解反应在摩尔比为1:6.8,温度为240到250摄氏度下反应2小时,得到牛磺酸钠的产率为80%。美国专利号1,999,614中描述,在氨解反应中加入催化剂,如硫酸钠,亚硫酸钠和碳酸钠,得到牛磺酸钠和二牛磺酸钠的混合物,产率高达97%,但是牛磺酸钠和二牛磺酸钠在混合物中的比例没有具体说明。
DD219023详细描述了羟乙基磺酸钠氨解反应产品的具体组成。当羟乙基磺酸钠和25%质量浓度的氨水的氨解反应,以1:9的摩尔比例,并用硫酸钠和氢氧化钠为催化剂,在280摄氏度下反应45分钟,得到的产品中含有71%牛磺酸钠和29%二牛磺酸钠及三牛磺酸钠。
WO01/77071中使用的方法是,在反应介质存在条件下,将牛磺酸钠水溶液加热到210摄氏度,得到牛磺酸钠和二牛磺酸钠的混合物。
由以上这些已知的合成工艺可以总结出,羟乙基磺酸钠氨解反应不可避免地会得到牛磺酸钠、二牛磺酸钠和三牛磺酸钠的混合物,其中牛磺酸钠的含量不会超过80%。
美国专利号2,693,488发明了一种使用离子交换树脂,由牛磺酸钠制备牛磺酸的方法,首先使用强酸阳离子型交换树脂,然后使用碱性阴离子交换树脂。这个过程复杂,且在每个生产循环中,离子交换树脂的再生需要使用大量的酸和碱。
另一方面,中国专利CN101508657,CN10158658,CN10158659和CN101486669阐述了一种使用硫酸中和牛磺酸钠从而得到牛磺酸和硫酸钠的方法,冷却之后通过将晶体悬浊液过滤,可以很容易地得到牛磺酸粗品。但是,废弃的滤液中仍然含有牛磺酸,硫酸钠和其他有机杂质,为二牛磺酸钠和三牛磺酸钠的混合物。
美国专利号9,428,450和美国专利号9,428,451解决了现有环氧乙烷生产牛磺酸工艺的部分问题,主要是将羟乙基磺酸碱金属盐氨解反应的副产物,即二牛磺酸碱金属盐和三牛磺盐碱金属盐,转化为牛磺酸碱金属盐。从羟乙基磺酸钠生产牛磺酸的整体收率提高到从85%到几乎定量。
美国专利号8,609,890公开了一种使用羟乙基磺酸或二氧化硫来中和牛磺酸碱金属盐以生产牛磺酸并再生羟乙基磺酸盐的方法。美国专利9,108,907号还公开了一种使用由乙醇制备的羟乙基磺酸来中和牛磺酸碱金属盐再生羟乙基磺酸碱金属盐的方法。目的是减少或消除在生产牛磺酸中使用硫酸作为酸化剂。
美国专利号9,061,976公开了通过使用二氧化硫作为酸并通过将氨解反应的副产物,二牛磺酸碱金属盐和三牛磺盐碱金属盐,转化为牛磺酸碱金属盐的综合生产方案。总产量提高到90%以上,并且从生产过程中消除了硫酸碱金属盐。该方法的一个缺点是使用气态的二氧化硫并且产品带有轻微异味。另一个显著的缺点是来自该方法的牛磺酸产品可能含有痕量的亚硫酸碱金属盐,这可能是某些人的过敏原。
美国专利申请号15/238,621公开了一种以大于90%至几乎定量的高总产率从羟乙基磺酸生产牛磺酸的循环方法,而不产生无机盐作为副产物。然而,起始原料羟乙基磺酸难以在商业上获得,并且是通过羟乙基磺酸碱金属盐的双极膜电渗析的昂贵工艺生产的。
CN 101717353A描述了一个制备牛磺酸的方法:(1)环氧乙烷与亚硫酸铵反应产生羟乙基磺酸铵和氨;(2)将得到的产物氨解为牛磺酸铵;(3)用硫酸酸化,得到牛磺酸。然而,反复的尝试在公开的条件下不能产生任何牛磺酸。
本发明的一个目标是克服现有的生产牛磺酸方法的缺点,并且还提供了从以下描述中将变得显而易见的优点。
本发明的另一个目标是公开一种高总产率(即大于90%至几乎定量)从羟乙基磺酸铵生产牛磺酸的方法,而且不产生任何无机盐作为副产物。
原料羟乙基磺酸铵可以根据现有技术使环氧乙烷与亚硫酸氢铵反应而容易且经济地制备,例如美国专利号5,646,320和美国专利号5,739,365。
根据本发明的方法,将羟乙基磺酸碱金属盐或再生的羟乙基磺酸碱金属盐,二牛磺酸和三牛磺酸碱金属盐和过量氨混合,在一种或多种催化剂的存在下,连续进行氨解反应,形成牛磺酸碱金属盐,二牛磺酸碱金属盐,和三牛磺酸碱金属盐。在氨解溶液中加入羟乙基磺酸铵后,除去过量的氨,得到结晶牛磺酸和羟乙基磺酸碱金属盐,二牛磺酸和三牛磺酸碱金属盐溶液。在牛磺酸的固液分离后,将母液直接循环至氨解步骤。
使用羟乙基磺酸铵作为起始原料的优点变得明显,因为在分离出结晶牛磺酸后不需要分离作为副产物的碱金属盐,母液中只含有羟乙基磺酸碱金属盐,二牛磺酸碱金属盐,和三牛磺酸碱金属盐。
发明内容
本发明公开一种从羟乙基磺酸铵生产牛磺酸的循环方法,其整体总产率大于90%至接近定量,而且不产生任何无机盐副产物。
原料羟乙基磺酸铵是通过环氧乙烷与亚硫酸氢铵按下面的反应制得:
在溶液中生产的羟乙基磺酸铵可直接用于生产牛磺酸。优选地,通过将溶液浓缩以获得结晶原料来纯化羟乙基磺酸铵。当固体羟乙基磺酸铵用于生产牛磺酸时,产生的牛磺酸的质量得到改善,并且循环过程几乎不需要母液的排放。
根据本发明的方法,将羟乙基磺酸碱金属盐或再生的羟乙基磺酸碱金盐,二牛磺酸碱金属盐,和三牛磺酸碱金属盐与过量的氨混合。在反应溶液中加入二牛磺酸碱金属盐,和三牛磺酸碱金属盐可抑制副产物的形成,提高生产产率,并大幅减少或消除生产过程中的废物排放。碱金属是锂,钠或钾。
氨解反应是在160℃至260℃的温度下,在自生至260巴的压力下进行1-6小时。
氨解反应后,向氨解溶液中加入羟乙基磺酸铵,与牛磺酸碱金属盐反应。过量的氨从反应溶液中排出并回收再利用。浓缩冷却后得到牛磺酸的结晶悬浮液,溶液则含有二牛磺酸碱金属盐,三牛磺酸碱金属盐,痕量的未反应的羟乙基磺酸碱金属盐。
羟乙基磺酸铵和氨解液中牛磺酸碱金属盐的的摩尔比为0.1~10。优选的摩尔比为0.5~1.5,更优选为0.9~1.1,最优选为0.95~1.05。当该比例低于当量时,除去氨后的最终pH高于7,并且在溶液中将残留更多的牛磺酸。当该比例大于当量时,最终pH在5至6的期望范围内,但在氨解阶段期间将消耗额外的碱金属氢氧化物。
在氨解阶段形成的牛磺酸碱金属盐与羟乙基磺酸铵的反应按照下面方程式进行:
从上述反应释放出的氨和过量的氨除去可以通过加热或用蒸汽汽提来进行。完全除去氨后,强碱性溶液变为中性,生成结晶牛磺酸和含有羟乙基磺酸碱金属盐,二牛磺酸碱金属盐,三牛磺酸碱金属盐,痕量的未反应的羟乙基磺酸碱金属盐的溶液。初始悬浮液可以先浓缩,然后冷却以使牛磺酸结晶。牛磺酸通过固液分离得到。
在牛磺酸分离后,含有羟乙基磺酸碱金属盐,二牛磺酸碱金属盐,三牛磺酸碱金属盐的母液用氨饱和并进行氨解反应。
显然,反应体系中的碱金属在该生产过程中连续循环使用,只有羟乙磺酸铵转化为牛磺酸。循环过程的净反应是:
在氢氧化物,碳酸盐,碳酸氢盐,硫酸氢盐,硫酸盐,亚硫酸氢盐,亚硫酸盐,硝酸盐,磷酸盐,氯酸盐和高氯酸盐的碱金属盐中发现氨解反应的有用和有效的催化剂。这些盐是氢氧化钠,氢氧化锂,氢氧化钾,碳酸锂,碳酸氢锂,碳酸氢钠,碳酸氢钠,碳酸氢钾,碳酸锂,碳酸钠,碳酸钾,硫酸锂,硫酸钠,硫酸钾,磷酸锂,磷酸钠,磷酸钾,亚硫酸锂,亚硫酸钠和亚硫酸钾。
在二牛磺酸碱金属盐和三牛磺酸碱金属盐存在下,羟乙基磺酸碱金属盐的氨解反应催化剂可以是一种组分或两种或更多种组分的组合。优选的催化剂是碱金属氢氧化物,最优选的催化剂是氢氧化钠。
所使用的催化剂的量没有限制,但催化剂对羟乙基磺酸碱金属盐的摩尔比通常为0.01-10。该比例优选为0.01~1,更优选为0.1~0.5,最优选为0.2~0.3。本领域技术人员可以选择合适量的催化剂使得氨解反应在期望的时间内完成。
作为催化剂,将碱金属氢氧化物引入反应体系中,需要额外的羟乙基磺酸铵来中和。结果是循环过程中碱金属的积累增加。因此优选在生产过程内产生碱金属氢氧化物。一种方便的方法是通过使用双极膜电渗析法将母液中的二牛磺酸碱金属盐分解成酸组分,二牛磺酸和碱金属氢氧化物组分。在使用碱金属氢氧化物作为氨解反应的催化剂,使用二牛磺酸溶液作为酸。
根据本发明的循环过程,牛磺酸的产率大于90%到几乎定量,并且不产生除了循环系统的少量排杂之外的任何废物。
根据本发明的方法可以不连续地,半连续地和连续地进行。
附图说明
图1描述了由羟乙基磺酸铵生产牛磺酸的流程图的一个实施方案。
实例
以下实施例说明了本发明的实施,但并不旨在限制本发明的范围。
实施例1
向2L高压釜中加入1200mL 24%氨溶液,296g羟乙基磺酸钠和2g氢氧化钠。将溶液在自生压力下加热至260℃2小时。冷却后,加入286.2g羟乙基磺酸铵,通过煮沸除去氨,使溶液的pH达到pH6.5。加热除去过量的氨后,浓缩并冷却至室温,得到结晶牛磺酸的悬浮液。通过过滤回收牛磺酸并干燥至189.3g。牛磺酸回收率为75.7%。
实施例2
向实施例1的母液中加入340g气态氨,用去离子水将总体积调节至1500mL,然后加入12.4g氢氧化钠。将溶液置于2L高压釜中,并如实施例1所述进行氨解反应和用羟乙基磺酸铵处理。
基于所用的羟乙基磺酸铵,干燥后得到241.2g的牛磺酸,收率为96.2%。
实施例3~8
牛磺酸分离后的母液在用氨饱和后,在15g氢氧化钠的存在下反复进行5次的氨解反应,基于所用的羟乙基磺酸铵,总牛磺酸的产率为96.4%。
应当理解,前述实施例,附图和说明仅用于说明的目的,并且本发明的各种改进对于本领域技术人员将是不言而喻的。这些改进将被包括在本申请的精神和范围以及所附权利要求的范围内。
Claims (3)
1.一种从牛磺酸碱金属盐或牛磺酸碱金属盐、二牛磺酸碱金属盐和三牛磺酸碱金属盐的混合物制备牛磺酸的方法,包括:
(a)向牛磺酸碱金属盐或牛磺酸碱金属盐、二牛磺酸碱金属盐和三牛磺酸碱金属盐的混合物溶液中加入羟乙基磺酸铵产生羟乙基磺酸碱金属盐和牛磺酸铵,其中,加入的羟乙基磺酸铵的量与牛磺酸碱金属盐的摩尔比为0.1~10;
(b)通过加热分解步骤(a)产生的牛磺酸铵并除去氨,产生牛磺酸;
(c)通过固液分离分离出步骤(b)产生的牛磺酸。
2.根据权利要求1所述的方法,其特征在于,通过氨解羟乙基磺酸碱金属盐生成牛磺酸碱金属盐、二牛磺酸碱金属盐和三牛磺酸碱金属盐的所述混合物。
3.根据权利要求1所述的方法,其特征在于,碱金属是锂、钠或钾。
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