CN114671784A - Method for preparing taurine from acrylonitrile - Google Patents
Method for preparing taurine from acrylonitrile Download PDFInfo
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- CN114671784A CN114671784A CN202210218869.8A CN202210218869A CN114671784A CN 114671784 A CN114671784 A CN 114671784A CN 202210218869 A CN202210218869 A CN 202210218869A CN 114671784 A CN114671784 A CN 114671784A
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- CN
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- Prior art keywords
- sodium
- acrylonitrile
- taurine
- amino
- propanesulfonate
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- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229960003080 taurine Drugs 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 40
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 22
- 108090000790 Enzymes Proteins 0.000 claims description 18
- 102000004190 Enzymes Human genes 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 108010033272 Nitrilase Proteins 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 10
- 238000006277 sulfonation reaction Methods 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 239000001963 growth medium Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 8
- 239000011942 biocatalyst Substances 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- 241000588724 Escherichia coli Species 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000001888 Peptone Substances 0.000 claims description 5
- 108010080698 Peptones Proteins 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 5
- 238000000909 electrodialysis Methods 0.000 claims description 5
- 238000000855 fermentation Methods 0.000 claims description 5
- 230000004151 fermentation Effects 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 235000019319 peptone Nutrition 0.000 claims description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 5
- 238000012258 culturing Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 2
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- HFFHSQIXUBWHQS-UHFFFAOYSA-M sodium;3-cyanopropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCC#N HFFHSQIXUBWHQS-UHFFFAOYSA-M 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 2
- OWYQKLGWPKAMLR-UHFFFAOYSA-M sodium;3-amino-3-oxopropane-1-sulfonate Chemical compound [Na+].NC(=O)CCS([O-])(=O)=O OWYQKLGWPKAMLR-UHFFFAOYSA-M 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000012043 crude product Substances 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 229940104256 sodium taurate Drugs 0.000 description 5
- GWLWWNLFFNJPDP-UHFFFAOYSA-M sodium;2-aminoethanesulfonate Chemical compound [Na+].NCCS([O-])(=O)=O GWLWWNLFFNJPDP-UHFFFAOYSA-M 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005915 ammonolysis reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 108090000604 Hydrolases Proteins 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- ZKTDJISAFXRWKI-UHFFFAOYSA-N cyano propane-1-sulfonate Chemical compound C(#N)OS(=O)(=O)CCC ZKTDJISAFXRWKI-UHFFFAOYSA-N 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229940045998 sodium isethionate Drugs 0.000 description 2
- LADXKQRVAFSPTR-UHFFFAOYSA-M sodium;2-hydroxyethanesulfonate Chemical compound [Na+].OCCS([O-])(=O)=O LADXKQRVAFSPTR-UHFFFAOYSA-M 0.000 description 2
- NPAWNPCNZAPTKA-UHFFFAOYSA-M sodium;propane-1-sulfonate Chemical compound [Na+].CCCS([O-])(=O)=O NPAWNPCNZAPTKA-UHFFFAOYSA-M 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- -1 3-cyano propanesulfonic acid sodium Chemical compound 0.000 description 1
- 206010004542 Bezoar Diseases 0.000 description 1
- 238000007167 Hofmann rearrangement reaction Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003797 essential amino acid Substances 0.000 description 1
- 235000020776 essential amino acid Nutrition 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- WSYUEVRAMDSJKL-UHFFFAOYSA-N ethanolamine-o-sulfate Chemical compound NCCOS(O)(=O)=O WSYUEVRAMDSJKL-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 210000003754 fetus Anatomy 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000006152 selective media Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
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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
-
- 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
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P13/00—Preparation of nitrogen-containing organic compounds
- C12P13/02—Amides, e.g. chloramphenicol or polyamides; Imides or polyimides; Urethanes, i.e. compounds comprising N-C=O structural element or polyurethanes
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing taurine from acrylonitrile, which comprises the steps of sulfonating the acrylonitrile, obtaining an intermediate by a biological hydrolysis method, carrying out Hofmann degradation on the intermediate, and then carrying out neutralization, crystallization separation and the like to obtain a finished product taurine. Compared with the traditional process for preparing taurine, the method has the advantages of mild reaction conditions, safer preparation process, lower energy consumption and lower environmental protection pressure, and obviously improves the yield of taurine.
Description
Technical Field
The application belongs to the field of chemical industry, and particularly relates to a method for preparing taurine from acrylonitrile.
Background
Taurine (Taurine), also known as beta-aminoethanesulfonic acid, was first isolated from bezoar and is known as such. The pure product is colorless or white rhombic crystal, and has no odor. Taurine is essential amino acid for human body, and has important effect on development of nervous system of fetus and infant. Taurine can be widely used in the fields of medicine, food additive, fluorescent whitening agent, organic synthesis and the like, and also can be used as biochemical reagent, wetting agent, pH buffering agent and the like. The chemical synthesis method of taurine currently has more than 20 methods according to different raw materials and processes. However, because of the limitations of raw material sources, production cost, product yield, synthesis process conditions and equipment requirements, two methods are really available for industrial production:
The ethanolamine method comprises the steps of taking ethanolamine as a raw material, synthesizing taurine in two steps, taking ethanolamine, sulfuric acid and sodium sulfite as reaction raw materials in the synthetic route, firstly carrying out esterification reaction on the ethanolamine and the sulfuric acid to generate an intermediate 2-amino-ethyl sulfate, and then carrying out sulfonation reaction on the intermediate and the sodium sulfite to synthesize the taurine.
However, the esterification and sulfonation reactions are reversible reactions, resulting in a low ethanolamine conversion and reaction yield of only 70%; a large amount of sodium sulfate waste salt is generated in the synthesis process, so that the yield and quality of the product are influenced, and the environmental protection pressure is large; the reaction temperature is high, the reaction period is long, and the energy consumption is extremely high; therefore, the ethanolamine process has been gradually eliminated.
Ethylene oxide process: firstly, ethylene oxide and sodium bisulfite are subjected to ring-opening addition to generate sodium isethionate, then the sodium isethionate is reacted with liquid ammonia under the conditions of high temperature and high pressure to generate sodium taurate, and the sodium taurate is acidified to generate taurine.
However, ethylene oxide is flammable, explosive and toxic, so that potential safety hazards exist in the operation process; the second step of generating sodium taurate requires high temperature and high pressure; the liquid ammonia dosage is higher; ethylene oxide generates side reaction in water to generate organic impurities such as ethylene glycol, ethanolamine and the like which are difficult to remove, and the recovery and utilization rate of mother liquor is influenced.
Chinese patent CN105732440A mentions that in the ammonolysis reaction process, a catalyst containing alkali metal, transition metal or rare earth metal can be added to improve the yield of sodium taurate, but the reaction still requires high temperature and high pressure, and the conditions are still harsh.
Chinese patent CN107056659A mentions that the catalyst containing alkali metal, transition metal or rare earth metal is also added during the ammonolysis reaction, however, the ammonolysis reaction still requires high temperature and high pressure, and the pressure is only 5MPa lower than that of patent CN105732440A, and the conditions of the patent are only slightly milder than that of patent CN 105732440A.
The U.S. Pat. No. 3, 20160355470, 1 mentions that the addition of NaOH as a catalyst in the ammonolysis reaction increases the yield of sodium taurate to more than 90%, but still requires high temperature and high pressure.
In conclusion, in the existing taurine preparation process, the ethanolamine method has low yield, high energy consumption, more generated waste salt and high environmental protection pressure, and the ethylene oxide method has harsh reaction conditions, so the preparation process needs to be improved to improve the yield, reduce the energy consumption in the production process and reduce the production cost.
The invention content is as follows:
aiming at the problems, the invention provides a method for preparing taurine by sulfonating acrylonitrile and using biological enzyme to catalyze hydration to obtain 3-amino-3-ketone-sodium propanesulfonate, wherein the yield of the preparation process is higher than that of an ethanolamine method, the reaction condition is milder than that of the ethanolamine method, the energy consumption is lower, and compared with an ethylene oxide method, the method has the advantages of safer raw materials, less reaction impurities and lower environmental protection pressure.
In order to achieve the purpose, the technical scheme adopted by the application is as follows:
a method for preparing taurine from acrylonitrile comprises the following specific process flows:
a method for preparing taurine from acrylonitrile comprises the following specific steps:
(a) dropping acrylonitrile into a sulfonation reagent aqueous solution at 35-90 ℃ to obtain 3-cyano sodium propanesulfonate;
(b) under the action of biological hydrolase, preserving the heat of 3-cyano sodium propanesulfonate at 30-40 ℃ to obtain a 3-amino-3-ketone-sodium propanesulfonate intermediate in a biological hydrolysis mode;
(c) adding sodium hypochlorite into the 3-amido-3-ketone-sodium propane sulfonate intermediate water solution at the temperature of-10 to 30 ℃;
(d) adding liquid caustic soda into the aqueous solution obtained in the step (c), heating to 60-90 ℃, and preserving heat for 1-3 h;
(e) and (3) adding hydrochloric acid into the reaction liquid obtained in the step (d) to adjust ph to 3.0-5.3, concentrating and filtering the reaction liquid obtained in the step (e) at high temperature, crystallizing at low temperature, dissolving, and performing electrodialysis to obtain a pure taurine product.
The sulfonation reagent selected in the step (a) is one or more of sodium bisulfite, sodium sulfite, sodium metabisulfite, sodium thiosulfate and a combination of sulfur dioxide and alkali system;
The sulfur dioxide and alkali system is a system of sulfur dioxide and sodium carbonate, a system of sulfur dioxide and sodium hydroxide or a system of sulfur dioxide and triethylamine.
The biological hydrolase in the step (b) is nitrilase which is purchased from Sigma Aldrich, and is preferably the nitrilase cultured by using 3-cyano sodium propanesulfonate as a selective medium.
In the step (c), the effective chlorine of the sodium hypochlorite is 6-12%, and the dosage of the effective chlorine is 1.0-1.2 times of the molar quantity of the 3-amido-3-ketone-sodium propanesulfonate;
in the step (d), the concentration of the liquid caustic soda is 32%, and the dosage of the liquid caustic soda is 1.0-3.0 times, preferably 1.2-2.2 times of the molar weight of the 3-amido-3-ketone-sodium propanesulfonate.
Because of the low yield of acrylamide sulfonation, acrylonitrile is used as the raw material substrate in order to avoid the loss of acrylamide sulfonation. The yield can be 99% with the sulphonation reagent.
In the step of converting nitrile into amide, the nitrilase is used for hydrolyzing the sulfonated product to generate a 3-amino-3-ketone-sodium propanesulfonate intermediate, the nitrilase selectivity difference is used, the purchased nitrilase (expressed in E. coli, more than or equal to 2.0U/mg) is cultured for enzyme-producing cells, 3-sodium cyanopropanesulfonate is added into a basal culture medium as a selective culture medium (glucose 2%, peptone 0.9%, sodium 3-cyanopropanesulfonate concentration 0.4%, pH 7.0), and the fermentation liquor is centrifugally separated to obtain the enzyme-containing cell biocatalyst, wherein the yield can reach 99%.
The detailed improvement of the Hofmann rearrangement process can achieve 98% of yield, so that the total yield can achieve 96%. However, sodium chloride is inevitably introduced due to the use of sodium hypochlorite, and the sodium chloride in the taurine crystals is difficult to remove after high-temperature filtration.
Detailed Description
The preparation of the taurine intermediate 3-amino-3-keto-sodium propanesulfonate and taurine of the present invention will be further described below by way of examples.
Example 1
Dissolving 104.0 g (1 mol) of sodium bisulfite in 300 mL of water to prepare a sulfonation reagent aqueous solution, dripping 53.0 g (1 mol) of acrylonitrile into the sodium bisulfite aqueous solution heated to 35 ℃, dripping for 1 hour, and after dripping, keeping the temperature to react for one hour to obtain the 3-cyano sodium propanesulfonate aqueous solution with the liquid phase yield of 92 percent. The method comprises the steps of culturing enzyme-producing cells by using purchased nitrilase (expressed in E. coli, more than or equal to 2.0U/mg), adding 3-sodium nitrilopropionate into a basic culture medium as a selective culture medium (glucose 2%, peptone 0.9%, 3-sodium nitrilopropionate 0.4% and pH 7.0), and performing centrifugal separation on fermentation liquor to obtain the enzyme-containing cell biocatalyst. 100mg of the catalyst is added into the reaction liquid, heated to 40 ℃, stirred for 2 hours to obtain 3-amino-3-ketone-sodium propanesulfonate solution, and after concentration and recrystallization, 159.3 g (0.91 mol) of 3-amino-3-ketone-sodium propanesulfonate intermediate is obtained, with the yield accounting for 99 percent of 3-nitrile group sodium propanesulfonate and 91 percent of acrylonitrile. 159.3 g (0.91 mol) of intermediate 3-amino-3-ketone-sodium propanesulfonate is dissolved in 400 mL of water, 807.4 g (0.91 mol) of sodium hypochlorite solution of 8.0% of available chlorine is added at the temperature of 0 ℃, 227.4g (1.82 mol) of 32% liquid caustic soda is added dropwise after the dropwise addition is finished, then the temperature is raised to 70 ℃, the temperature is kept for one hour, and hydrochloric acid is added to adjust the pH value to 3.5. The taurine crude product is obtained through concentration, hot filtration and low-temperature crystallization, and the taurine crude product is dissolved in water, and after sodium chloride is removed through an electrodialysis device, the taurine crude product is concentrated and crystallized to obtain 104.6 g (0.84 mol) of taurine, the yield is 92 percent, and the yield is 90.1 percent calculated by acrylonitrile.
Example 2
Dissolving 126.0 g (1 mol) of sodium sulfite in 300 mL of water to prepare a sulfonation reagent aqueous solution, dripping 53.0 g (1 mol) of acrylonitrile into the sodium sulfite aqueous solution heated to 50 ℃, dripping for 1 hour, and after dripping is finished, carrying out heat preservation reaction for one hour to obtain a 3-cyano propanesulfonic acid sodium aqueous solution, wherein the liquid phase yield is 95%. The method comprises the steps of culturing enzyme-producing cells by using purchased nitrilase (expressed in E. coli, more than or equal to 2.0U/mg), adding 3-sodium nitrilopropionate into a basic culture medium as a selective culture medium (glucose 2%, peptone 0.9%, 3-sodium nitrilopropionate 0.4% and pH 7.0), and performing centrifugal separation on fermentation liquor to obtain the enzyme-containing cell biocatalyst. 100mg of the catalyst is added into the reaction liquid, heated to 40 ℃, stirred for 2 hours to obtain 3-amino-3-ketone-sodium propanesulfonate solution, and after concentration and recrystallization, 164.6 g (0.94 mol) of 3-amino-3-ketone-sodium propanesulfonate intermediate is obtained, with the yield accounting for 99 percent of 3-nitrile group sodium propanesulfonate and 94 percent of acrylonitrile. Then 164.6 g (0.94 mol) of intermediate 3-amino-3-ketone-sodium propanesulfonate is dissolved in 400 mL of water, 976.3 g (1.03 mol) of sodium hypochlorite solution of 8.0% of available chlorine is added under the condition of 0 ℃, after the dropwise addition is finished, 234.9 g (1.88 mol) of 32% caustic soda liquid is dropwise added, then the temperature is raised to 70 ℃, the temperature is kept for one hour, and the pH is adjusted to 4.0. The taurine crude product is obtained through concentration, hot filtration and low-temperature crystallization, and the taurine crude product is dissolved in water, and after sodium chloride is removed through an electrodialysis device, the taurine crude product is concentrated and crystallized to obtain 108.1 g (0.89 mol) of taurine, the yield is 98 percent, and the yield is 93.1 percent calculated by acrylonitrile.
Example 3
Dissolving 53.0 g (0.5 mol) of sodium carbonate in 300 mL of water, introducing sulfur dioxide until the pH value is 7 to prepare a sulfonated reagent aqueous solution, dripping 53.0 g (1 mol) of acrylonitrile into the sulfur dioxide and sodium carbonate aqueous solution which is heated to 70 ℃ and has the pH value of 7, dripping for 1 hour, simultaneously introducing the sulfur dioxide to control the reaction pH value to be kept between 6 and 8, and carrying out heat preservation reaction for one hour after finishing dripping to obtain the 3-sodium cyanopropanesulfonate aqueous solution, wherein the liquid phase yield is 99 percent. The method comprises the steps of culturing enzyme-producing cells by using purchased nitrilase (expressed in E. coli, more than or equal to 2.0U/mg), adding 3-sodium nitrilopropionate into a basic culture medium as a selective culture medium (glucose 2%, peptone 0.9%, 3-sodium nitrilopropionate 0.4% and pH 7.0), and performing centrifugal separation on fermentation liquor to obtain the enzyme-containing cell biocatalyst. 100mg of the catalyst is added into the reaction liquid, the mixture is heated to 40 ℃ and stirred for 2 hours to obtain 3-amino-3-ketone-sodium propanesulfonate solution, and 171.5 g (0.98 mol) of 3-amino-3-ketone-sodium propanesulfonate intermediate is obtained after concentration and recrystallization, wherein the yield is 99 percent of 3-cyano sodium propanesulfonate and 98 percent of acrylonitrile. And then, dissolving 171.5 g (0.98 mol) of the intermediate 3-amino-3-ketone-sodium propanesulfonate in 400 mL of water, adding 637.5 g (1.08 mol) of a sodium hypochlorite solution containing 12.0% of available chlorine at the temperature of 0 ℃, dropwise adding 244.8 g (1.95 mol) of 32% liquid caustic soda after dropwise adding, then heating to 70 ℃, preserving the temperature for one hour, and adjusting the pH to 5.0. The taurine crude product is obtained by concentration, heat filtration and low temperature crystallization, and is dissolved in water to remove sodium chloride by an electrodialysis device, and then the concentration and crystallization are carried out to obtain 120.0 g (0.96 mol) of taurine with the yield of 98 percent, which is 96.1 percent calculated by acrylonitrile.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A method for preparing taurine from acrylonitrile is characterized by comprising the following specific process flows:
2. the method for preparing taurine from acrylonitrile according to claim 1, comprising the following steps:
(a) dripping acrylonitrile into a sulfonation reagent aqueous solution at the temperature of 35-90 ℃, and carrying out heat preservation reaction for 1h to obtain a 3-cyano sodium propanesulfonate aqueous solution;
(b) Adding a biocatalyst into the solution obtained in the step (a), keeping the temperature at 30-40 ℃, and stirring for 2 hours to obtain a 3-amino-3-ketone-sodium propanesulfonate intermediate;
(c) dissolving the intermediate 3-amino-3-ketone-sodium propanesulfonate in water, controlling the temperature to be minus 10-30 ℃, dropwise adding a sodium hypochlorite aqueous solution into the 3-amino-3-ketone-sodium propanesulfonate intermediate aqueous solution, and standing by after dropwise adding;
(d) adding liquid caustic soda into the aqueous solution obtained in the step (c), heating to 60-90 ℃, and preserving heat for 1-3 h;
(e) and (d) adding hydrochloric acid into the reaction liquid obtained in the step (d) to adjust the pH value to 3.0-5.3, concentrating and filtering the reaction liquid at high temperature, crystallizing at low temperature, dissolving, and performing electrodialysis to obtain a pure taurine product.
3. A process for preparing taurine from acrylonitrile as claimed in claim 2, wherein the sulfonation reagent selected in step (a) is one or more of sodium bisulfite, sodium sulfite, sodium metabisulfite, sodium thiosulfate or a combination of sulfur dioxide and a base system.
4. The method for preparing taurine from acrylonitrile according to claim 2, wherein the biocatalyst in step (b) is specifically prepared as follows:
The method comprises the steps of culturing enzyme-producing cells by using more than or equal to 2.0U/mg of purchased nitrilase, nitrilase recombiant and expressed in E.coli, adding 2% of glucose, 0.9% of peptone, 0.4% of sodium 3-cyanopropylsulfonate and pH 7.0 into a basic culture medium, and performing centrifugal separation on fermentation liquor to obtain the enzyme-containing cell biocatalyst which is nitrilase.
5. The method for preparing taurine from acrylonitrile as claimed in claim 2, wherein the amount of sodium hypochlorite available chlorine in step (c) is 6% -12% and is 1.0-1.2 times of the molar amount of 3-amino-3-keto-propanesulfonic acid sodium salt.
6. The method for preparing taurine from acrylonitrile according to claim 2, wherein the concentration of the liquid alkali in the step (d) is 32%, and the amount of the liquid alkali is 1.0 to 3.0 times of the molar amount of the 3-amino-3-keto-sodium propanesulfonate.
7. The method for preparing taurine from acrylonitrile according to claim 2, wherein the concentration of the liquid alkali in the step (d) is 32%, and the amount of the liquid alkali is 1.2 to 2.2 times of the molar amount of the 3-amino-3-keto-sodium propanesulfonate.
8. The method of claim 3, wherein the sulfur dioxide and base system is a system prepared by introducing sulfur dioxide into sodium carbonate solution, sodium hydroxide solution or triethylamine solution.
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| US4256660A (en) * | 1979-05-31 | 1981-03-17 | Allied Colloids Limited | Sulphonated derivatives of acrylamide and their preparation |
| CN101362709A (en) * | 2008-07-31 | 2009-02-11 | 杭州福斯特药业有限公司 | 3-amino propanesulfonic acid preparation method |
| CN111757940A (en) * | 2017-11-14 | 2020-10-09 | 哥伦比亚有限公司 | Microbiological method for producing amides |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4256660A (en) * | 1979-05-31 | 1981-03-17 | Allied Colloids Limited | Sulphonated derivatives of acrylamide and their preparation |
| CN101362709A (en) * | 2008-07-31 | 2009-02-11 | 杭州福斯特药业有限公司 | 3-amino propanesulfonic acid preparation method |
| CN111757940A (en) * | 2017-11-14 | 2020-10-09 | 哥伦比亚有限公司 | Microbiological method for producing amides |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023109204A1 (en) * | 2021-12-18 | 2023-06-22 | 青岛科技大学 | Sulfonation method for unsaturated alkane of electron-withdrawing group |
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