WO2021108179A1 - Procédé de sulfonation d'ester sulfonique d'aminoéthylène pour produire de la taurine - Google Patents

Procédé de sulfonation d'ester sulfonique d'aminoéthylène pour produire de la taurine Download PDF

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Publication number
WO2021108179A1
WO2021108179A1 PCT/US2020/061004 US2020061004W WO2021108179A1 WO 2021108179 A1 WO2021108179 A1 WO 2021108179A1 US 2020061004 W US2020061004 W US 2020061004W WO 2021108179 A1 WO2021108179 A1 WO 2021108179A1
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WIPO (PCT)
Prior art keywords
aes
taurine
sulfonation
sulfate ester
vessel
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PCT/US2020/061004
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English (en)
Inventor
Chi-Cheng MA
James Brazdil
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Archer Daniels Midland Company
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Publication of WO2021108179A1 publication Critical patent/WO2021108179A1/fr

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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
    • C07C303/32—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
    • C07C303/02—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
    • C07C303/42—Separation; Purification; Stabilisation; Use of additives
    • C07C303/44—Separation; Purification

Definitions

  • This invention relates to a continuous process for producing taurine from aminoethanol sulfate ester, also called 2-aminoethyl hydrogen sulfate ester (AES).
  • AES 2-aminoethyl hydrogen sulfate ester
  • Taurine also known as 2-aminoethanesulfonic acid
  • Taurine is an amino acid that is found in natural dietary sources, biosynthesized in the body and produced by chemical synthesis for commercial purposes.
  • Taurine is sometimes referred to as a conditional amino acid because it is derived from cysteine like other amino acids but lacks a carboxyl group that usually belongs to amino acids. Instead, it contains a sulfide group and can be called an amino sulfonic acid.
  • EO is reacted with sodium bisulfite to produce sodium isethionate, which is then converted via ammonolysis to sodium taurinate.
  • Sodium taurinate is then neutralized to produce taurine.
  • sodium taurinate is neutralized with sulfuric acid, then a mixture of taurine and sodium sulfate is obtained.
  • sodium taurinate may be neutralized with sulfur dioxide to obtain taurine and to regenerate sodium bisulfite.
  • the disadvantage of the EO method lies in the problematic quality of the product. More specifically, taurine produced via the EO method is a powder, and tends to form a hard cake over a short period of time during storage (in a matter of weeks), possibly due to the presence of unknown impurities.
  • the process involves some serious hazards from the viewpoint of safety since it uses, as raw material, EO, which has extremely strong toxicity and carcinogenicity and is difficult to transport and handle.
  • the reaction is carried out at very high temperature (220-280° C.) and pressure (>100 bars).
  • taurine in a conventional method using MEA as the starting material, taurine can be prepared by reacting MEA with sulfuric acid to obtain the intermediate 2- aminoethyl hydrogen sulfate ester (AES).
  • AES 2- aminoethyl hydrogen sulfate ester
  • the MEA method produces taurine in the form of needle crystal that has excellent stability during transportation and storage as compared to the taurine powder produced in the EO method.
  • An added advantage of the MEA method is the mild processing conditions as compared to the high temperature and pressures as required in the EO method.
  • a disadvantage of the MEA method is its higher cost of manufacture and higher capital expenditures as compared to the EO method.
  • a disadvantage of the MEA method is the lengthy time for the sulfonation stage, typically 35-40 hours, due to the slow reaction of AES and sodium sulfite.
  • the MEA method typically has a low product yield in the sulfonation step.
  • U.S. Patent 9,145,359 discloses a method for the production of taurine by a cyclic process of reacting monoethanolamine, sulfuric acid, and ammonium sulfite in the presence of additives to inhibit the hydrolysis of 2-aminoethyl hydrogen sulfate (AES) intermediate.
  • AES 2-aminoethyl hydrogen sulfate
  • the patent states that it has now been found that the yield of taurine can be drastically increased by strictly maintaining the pH of the reaction mixture from 6.0 to 8.0 and carrying out the sulfonation reaction at a temperature of 80 to 150° C.
  • the patent discloses examples wherein starting materials were reacted in an autoclave equipped with a stirrer for 24 hours at 110° C. under autogenous pressure for 24 hours, and examples wherein starting materials were reacted in the same autoclave for 18 hours at 120° C.
  • U.S. 10,131,621 has the same named inventor as U.S. 9,145,359.
  • 10,131,621 discloses an extraction process for recovering aminoalcohols and glycols from aqueous streams of taurine production.
  • the aqueous streams which contain aminoalcohols and/or glycols are first mixed with a base to increase pH and then extracted with C3-C6 alcohols, ketones, and ethers.
  • the aqueous streams are then returned to their respective cyclic process for the production of taurine.
  • the patent states that according to the MEA process disclosed in U.S. Pat. No.
  • Typical EO and MEA methods are batch type processes that do not allow for continuous production of taurine.
  • a process comprises continuously adding a first stream and a second stream to a sulfonation vessel, wherein the first stream comprises aminoethanol sulfate ester (AES) and the second stream comprises an aqueous solution of sodium sulfite.
  • AES aminoethanol sulfate ester
  • the process comprises continuously mixing the aminoethanol sulfate ester and the aqueous solution of sodium sulfite in the sulfonation vessel, thus producing a mixture.
  • the process comprises continuously subjecting the mixture to heat in the presence of an inert gas, thus converting the aminoethanol sulfate ester to taurine via sulfonation.
  • the process further comprises subjecting the mixture to a pressure greater than autogenous pressure.
  • the aminoethanol sulfate ester (AES) has a residence time in the sulfonation vessel of no more than four (4) hours.
  • the aminoethanol sulfate ester (AES) has a residence time in the sulfonation vessel of no more than two (2) hours, the heat is a temperature of 140-155° C, and the mixture is subjected to a pressure of at least 200 psi..
  • the process results in a taurine yield of at least 80%.
  • FIG. 1 is a process flow diagram of a continuous taurine production process in accordance with aspects of the invention.
  • FIG. 2 depicts a drying apparatus for water removal in accordance with aspects of the invention.
  • FIG. 3 depicts an apparatus for sulfonation in accordance with aspects of the invention.
  • a continuous process comprises mixing an aqueous solution of sodium sulfite with aminoethanol sulfate ester in a sulfonation vessel, thus producing a mixture, and heating the mixture in the presence of an inert gas, thus converting the aminoethanol sulfate ester via sulfonation to taurine.
  • the inert gas may be any suitable inert gas, including but not limited to nitrogen, helium, argon, and combinations thereof.
  • the inert gas is nitrogen.
  • the heating step is conducted at a temperature of at least 115° C. and a pressure greater than autogenous pressure. The presence of the inert gas subjects the mixture to the pressure greater than autogenous pressure.
  • the heating step is conducted at a pressure of at least 50 psi, more preferably at least 100 psi, and even more preferably at least 200 psi.
  • the process results in a taurine yield of at least 80%.
  • the process results in at least a 95% AES conversion to taurine.
  • the aminoethanol sulfate ester has a residence time of no more than four (4) hours in the vessel.
  • This residence time of no more than four (4) hours of the aminoethanol sulfate ester in the reaction vessel during sulfonation conversion to taurine is a substantially less than the period of time for sulfonation in conventional ME A methods.
  • the aminoethanol sulfate ester has a residence time of no more than two (2) hours in the vessel.
  • FIG. 1 is a process flow diagram of a continuous taurine production process in accordance with aspects of the invention.
  • a continuous taurine manufacturing process 100 comprises reacting step 102 wherein monoethanolamine (ME A) and sulfuric acid (H2SO4) are mixed and react to form the intermediate 2-aminoethyl hydrogen sulfate ester (AES).
  • Reacting step 102 may comprise continuously conveying a stream of MEA and a stream of sulfuric acid to an AES synthesis reactor, and continuously conveying effluent 120 out of that AES synthesis reactor.
  • Effluent 120 of reacting step 102 comprises AES and water.
  • Reacting step 102 is followed by water removal step 104, wherein water is removed from AES.
  • Water removal step 104 may be performed using a spray dryer or thin film evaporator.
  • Effluent 122 of water removal step 104 comprises AES.
  • effluent 122 comprising AES is then sent to a sulfonation step 106.
  • Sulfonation step 106 comprises reacting AES with sodium sulfite (Na 2 S0 3 ) to form taurine.
  • sodium sulfate (Na 2 S0 4 ) may also be formed.
  • Sulfonation step 106 may comprise using an upflow or downflow sulfonation reactor wherein effluent 122 comprising AES is continuously pumped to the bottom or top of the sulfonation reactor.
  • a stream 124 comprising aqueous sodium sulfite is continuously pumped to the bottom or top of the sulfonation reactor.
  • AES is continuously mixes and reacts with sodium sulfite present in the sulfonation reactor.
  • the sulfonation reactor may be sealed with a pressure head with an inert gas 126 (e.g., nitrogen gas).
  • Sulfonation step 106 comprises continuously subjecting the mixture of AES and sodium sulfite to heat in the presence of the inert gas. The heat may be a predetermined reaction temperature.
  • the mixture of AES and sodium sulfite is continuously subjected to a pressure greater than autogenous pressure.
  • the pressure may be at least 200 psi inert gas (e.g., N2).
  • the heat may be at least 115° C.
  • the heat may be at least 120° C.
  • the heat may be 120-155° C.
  • the heat may be 140-155° C.
  • Effluent 108 from sulfonation step 106 comprises taurine and may also comprise Na2S04and Na2S03, as well as unreacted MEA and AES. [0022] Effluent 108 from sulfonation step 106 may then be conveyed to chromatography step 110. In chromatography step 110, Na2SC and Na2SC>3 is separated from taurine in effluent 108.
  • Effluent 112 from chromatography step 110 comprises taurine and may be conveyed to crystallization step 114.
  • crystallization step 114 taurine in effluent 112 is crystallized.
  • Crystallization step may comprise cooling effluent 112 from an elevated temperature, e.g., about 100° C, to a lower temperature, e.g., about 28° C.
  • Crystallization step 114 may be preceded by a water removal step (not shown in FIG. 1) wherein water is removed from effluent 112, e.g., by distillation, thereby concentrating the amount of taurine in effluent 112 prior to crystallization.
  • Effluent 116 from crystallization step 114 comprises crystallized taurine and may be conveyed to filtration step 118.
  • filtration step 118 crystallized taurine is separated from unreacted MEA and AES. Unreacted MEA and AES may be recycled to reaction step 102 for synthesis of AES as previously described.
  • FIG. 2 depicts a drying apparatus 200 for water removal in accordance with aspects of the invention.
  • Drying apparatus 200 comprises spray dryer 202.
  • Drying apparatus 200 comprises drying gas 204.
  • Drying gas 204 may be an inert gas, e.g., N2.
  • Liquid feed 206 may be the same as effluent 120 shown in FIG. 1.
  • liquid feed 206 comprises AES formed in reacting step 102 shown in FIG. 1.
  • Spray dryer 202 may comprise drying chamber 210 and an atomizer 208 configured to atomize liquid feed 206.
  • Effluent 212 from spray dryer 202 may be conveyed to cyclone 214.
  • exhaust gas 216 is separated from effluent 222.
  • Effluent 222 exits cyclone 214 through opening 218.
  • Effluent 222, comprising AES may be collected in a collector 220.
  • Effluent 222 may be the same as effluent 122 shown in FIG. 1. Thus, effluent 222 comprising AES has less water than liquid fee 206.
  • FIG. 3 depicts apparatus 300 for sulfonation step 106 shown in FIG.
  • apparatus 300 may comprise an upflow sulfonation reactor 302.
  • sulfonation reactor may be a downflow sulfonation reactor.
  • Feed 304 in feed vessel 306 may be degassed by an inert gas prior to being conveyed out of feed vessel 306.
  • the inert gas may be any suitable inert gas, including but not limited to nitrogen, helium, argon, and combinations thereof. In a preferred embodiment, the inert gas is nitrogen.
  • Feed 304 is continuously conveyed out of feed vessel 306 by pump 308 to bottom 310 of upflow sulfonation reactor 302.
  • Feed 304 may be the same as effluent 222 shown in FIG. 2. Thus, feed 304 comprises AES. As shown in FIG. 3, AES may be continuously pumped to the bottom of the sulfonation reactor 302. In sulfonation reactor 302, AES reacts with sodium sulfite present in the sulfonation reactor 302 to form taurine.
  • Aqueous sodium sulfite 322 in vessel 324 may be degassed by an inert gas prior to being conveyed out of vessel 324.
  • the inert gas may be any suitable inert gas, including but not limited to nitrogen, helium, argon, and combinations thereof. In a preferred embodiment, the inert gas is nitrogen.
  • Aqueous sodium sulfite 322 is continuously conveyed out of vessel 324 as stream 326 by pump 328 to bottom 310 of upflow sulfonation reactor 302.
  • Stream 326 comprising aqueous sodium sulfite 322 may be the same as stream 124 shown in FIG. 1.
  • Sulfonation reactor 302 may be sealed with a pressure head with an inert gas, e.g., inert gas 330.
  • Inert gas 330 may be the same as inert gas 126 shown in FIG. 1.
  • sulfonation step 106 shown in FIG. 1 may be performed in apparatus 300 shown in FIG. 3.
  • Sulfonation reactor 302 may be operated by heating the reaction mixture of AES and aqueous sodium sulfite at a reaction temperature and under a reaction pressure, e.g., a reaction pressure of at least 200 psi inert gas (e.g., N2).
  • the reaction temperature may be at least 115° C. In an embodiment, the reaction temperature may be at least 120° C.
  • the reaction temperature may be 120-155° C. In a more preferred embodiment, the reaction temperature may be 150-155° C.
  • effluent 318 may be collected in vessel 320. Effluent 318 may be the same as effluent 108 shown in FIG. 1.
  • effluent 318 comprises taurine, and may also comprise Na2S04 and Na2S03, as well as unreacted MEA and AES.
  • Exhaust gas 312 comprising inert gas may exit sulfonation reactor 302 through conduit 314 as may be desired, e.g., to purge materials in sulfonation reactor, or maintain a predetermined pressure in the sulfonation reactor 302.
  • a 250 ml round bottom flask was charged with 18 g of Na 2 S0 3 , 75 g water, and heated to 50° C to dissolve Na2S03. After dissolving Na2S03 in the water, 14 g of aminoethanol sulfate ester (AES) solid was added to flask. The flask was refluxed at 115° C for thirty (30) hours. After this time, the reaction was quenched by flash cooling in an ice bath. The product was analyzed by LC and 1 H, C13 NMR. Results from these analyses indicated a 73% AES conversion with 68% taurine yield. [0036] Example 4
  • Example 3 had a sulfonation stage with a reaction time of thirty (30) hours, and was not under pressure with N2 gas.
  • Examples 1, 2, 4, and 5, had much shorter sulfonation stages of either five (5) or (six) hours under pressure with N2 gas.
  • the following example demonstrates a method wherein a thin film evaporator is used to remove water.
  • the thin film evaporator may be used for the water removal step 104 shown in FIG. 1.
  • MEA (20 g) was charged into a 250 ml flask equipped with a stirrer and a thermometer.
  • H2SO4 36 g was slowly added into the flask over 30 minutes employing a dropping funnel.
  • the reactor used for the water removal step was placed in an ice/water bath during the initial H2SO4 addition to control the exothermic acid-base reaction.
  • Example 7 The following example demonstrates a method wherein a spray dryer is used to remove water.
  • the spray dryer may be used for the water removal step 104 shown in FIG. 1.
  • MEA (12 g) was charged into a 250 ml flask equipped with a stirrer and a thermometer.
  • H2SO4 (20 g) molar ratio (1:1) was slowly added into the flask over 30 minutes employing a dropping funnel.
  • LHSV Space Velocity

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé qui comprend l'ajout en continu d'un premier flux et d'un second flux à un récipient de sulfonation, le premier flux comprenant un ester sulfate d'aminoéthanol (AES) et le second flux comprenant une solution aqueuse de sulfite de sodium (Na2SO3). Le procédé comprend le mélange en continu de l'AES et de la solution aqueuse de Na2SO3 dans le récipient de sulfonation, ce qui permet de produire un mélange. Le procédé comprend la soumission en continu du mélange à de la chaleur en présence d'un gaz inerte, ce qui permet de convertir l'AES en taurine par sulfonation. Dans un aspect, l'AES a un temps de séjour ne dépassant pas quatre heures dans le récipient de sulfonation. Dans un aspect, l'étape de chauffage est réalisée à une température d'au moins 115° C et à une pression d'au moins 200 psi.
PCT/US2020/061004 2019-11-27 2020-11-18 Procédé de sulfonation d'ester sulfonique d'aminoéthylène pour produire de la taurine WO2021108179A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4657704A (en) * 1982-09-08 1987-04-14 Mitsui Toatsu Chemicals, Incorporated Production of aminoalkylsulfonic acids
US5250718A (en) * 1992-09-28 1993-10-05 Shell Oil Company Process for the preparation of secondary alkyl sulfate-containing surfactant compositions
CN101100449A (zh) * 2007-08-03 2008-01-09 江苏远洋化学有限公司 一种牛磺酸的合成方法
CN102285905A (zh) * 2011-07-05 2011-12-21 薛荔 牛磺酸的合成方法
US8609890B1 (en) * 2011-09-06 2013-12-17 Songzhou Hu Cyclic process for the production of taurine
US20150183731A1 (en) * 2013-12-30 2015-07-02 Songzhou Hu Cyclic process for the production of taurine from monoethanolamine
US20160340301A1 (en) * 2014-04-18 2016-11-24 Songzhou Hu Cyclic process for production of taurine from alkali vinyl sulfonate
CN106810472A (zh) * 2015-11-27 2017-06-09 姜殿凯 一种改进的牛磺酸生产工艺

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4657704A (en) * 1982-09-08 1987-04-14 Mitsui Toatsu Chemicals, Incorporated Production of aminoalkylsulfonic acids
US5250718A (en) * 1992-09-28 1993-10-05 Shell Oil Company Process for the preparation of secondary alkyl sulfate-containing surfactant compositions
CN101100449A (zh) * 2007-08-03 2008-01-09 江苏远洋化学有限公司 一种牛磺酸的合成方法
CN102285905A (zh) * 2011-07-05 2011-12-21 薛荔 牛磺酸的合成方法
US8609890B1 (en) * 2011-09-06 2013-12-17 Songzhou Hu Cyclic process for the production of taurine
US20150183731A1 (en) * 2013-12-30 2015-07-02 Songzhou Hu Cyclic process for the production of taurine from monoethanolamine
US20160340301A1 (en) * 2014-04-18 2016-11-24 Songzhou Hu Cyclic process for production of taurine from alkali vinyl sulfonate
CN106810472A (zh) * 2015-11-27 2017-06-09 姜殿凯 一种改进的牛磺酸生产工艺

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MA C.-C. ET AL.: "Continuous Process for the Production of Taurine from Monoethanolamine", INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, vol. 59, no. issue 29, 24 June 2020 (2020-06-24), pages 13007 - 13015, XP055830933, DOI: 10.1021/acs.iecr.0c02277 *
WU Y. ET AL.: "Comparison of Upflow and Downflow Two-Phase Flow Packed-Bed Reactors with and without Fines: Experimental Observations", INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, vol. 35, no. issue 2, 1996, pages 397 - 405, XP055830932, DOI: 10.1021/ie950318d *

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