WO2021128917A1 - Système de réaction d'ammonolyse continue, procédé de préparation de sel de taurine-métal alcalin et de taurine - Google Patents

Système de réaction d'ammonolyse continue, procédé de préparation de sel de taurine-métal alcalin et de taurine Download PDF

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WO2021128917A1
WO2021128917A1 PCT/CN2020/112059 CN2020112059W WO2021128917A1 WO 2021128917 A1 WO2021128917 A1 WO 2021128917A1 CN 2020112059 W CN2020112059 W CN 2020112059W WO 2021128917 A1 WO2021128917 A1 WO 2021128917A1
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ammoniating
autoclave
ammonia
taurine
alkali metal
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Chinese (zh)
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徐淞华
吴晓东
何孝祥
姚祥华
彭俊华
邱贵生
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ZHEJIANG NHU PHARMACEUTICAL CO Ltd
Shangyu NHU Biological Chemical Co Ltd
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ZHEJIANG NHU PHARMACEUTICAL CO Ltd
Shangyu NHU Biological Chemical Co Ltd
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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
    • C07C303/04—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 by substitution of hydrogen atoms by sulfo or halosulfonyl groups
    • C07C303/06—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 by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
    • C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton

Definitions

  • This application relates to the technical field of taurine, in particular to a continuous ammonolysis reaction system, an alkali metal salt of taurine and a preparation method of taurine.
  • Taurine also known as ⁇ -aminoethanesulfonic acid, is a sulfur-containing non-protein amino acid. It is widely used in the fields of medicine, food additives, fluorescent whitening agents, organic synthesis, etc.
  • the preparation methods include ethylene oxide method, cattle The ammonium sulfonate method, the monoethanolamine method and the ethanol method, etc.
  • the ethylene oxide method is the main method for preparing taurine at present, and among the ethylene oxide method, the ammonolysis reaction is the most studied, mainly because: first, sodium isethionate is at high temperature and high pressure.
  • by-products such as sodium ditaurate, which seriously affects the yield of the target product sodium taurate and the conversion rate of sodium isethionate; second, sodium ditaurate, etc.
  • By-products and residual sodium isethionate due to their high solubility in water, most of them remain in the mother liquor after acidification and separation. How to deal with the sodium isethionate and sodium ditaurate in the mother liquor
  • the by-product, sodium sulfate becomes a thorny issue.
  • the batch tank process is the most commonly used industrial ammonolysis operation mode at present.
  • the method is mature and reliable in technology, stable in operation, and the reaction yield is about 77%-80%.
  • its shortcomings are: 1.
  • the ammonia in the reaction system should be far excessive, so that the sodium isethionate and ammonia put into the ammoniation kettle, both The molar ratio is between 1:(10-30).
  • the concentration of ammonia and sodium isethionate in the material gradually decreases, the driving force of the reaction becomes smaller, and a longer reaction time needs to be maintained, which reduces the production efficiency.
  • Intermittent kettle-type technology has low single-batch output and long production cycle. And intermittent production, high energy consumption, low efficiency, small equipment capacity, large recovery of ammonia, high ammonia consumption.
  • the traditional technology also transforms the production method of high-pressure reactor batch operation into pipelined continuous operation.
  • Zhu Shengdong disclosed the taurine ammoniation reaction pipeline technology in "Chemical Science and Technology" 2001, Vol. 9, No. 3, which is After 25% aqueous ammonia solution is mixed with 35% sodium hydroxysulfonate aqueous solution and a small amount of catalyst, it is pressurized from the storage tank to 18MPa-20MPa by the high-pressure corrosion-resistant pump, and then heated to 280°C by the preheater, and then enters the tubular reaction The reactor is reacted in a tubular reactor for 30 minutes, and the reacted materials are continuously flowed out, and the pressure is reduced and flashed to obtain the ammonolysis product.
  • Pipeline continuous operation has the characteristics of strong production capacity, short process cycle, and good stability.
  • the equipment not only has to withstand high operating temperature, but also withstand the high pressure load of fluid, and it is also accompanied by ammonia, etc. Erosion of corrosive media.
  • the pressure and temperature are too high, and the coking of the material is serious.
  • the heat utilization rate of the system is low. In the early stage, the material should be heated to 100-200°C before the reaction. The heat released by the reaction needs to be removed.
  • a continuous ammonolysis reaction system includes:
  • a high-pressure reaction device the high-pressure reaction device includes n ammoniating autoclaves, n ⁇ 2, the first ammoniating autoclave to the nth ammoniating autoclave are connected in series in sequence, and the ammoniating autoclave is A container for the ammonolysis reaction, wherein the ammonolysis reaction uses ammonia as an ammoniating agent, the first ammoniating autoclave is connected with a feeding device, the first ammoniating autoclave to the nth ammoniating The autoclaves are all connected with a first feed pipe, and each of the ammoniated autoclaves is connected with a second feed pipe;
  • a buffer device which is connected to the n-th ammoniating autoclave, and is used to receive the mixture material after the ammoniation reaction in the first to the n-th ammoniating autoclaves;
  • a flashing device the flashing device is connected with the buffering device, and is used to receive the mixed material in the buffering device and obtain an ammonolysis product through flashing.
  • the raw materials to be reacted in the decomposition reaction such as alkali metal isethionate, etc., so that the ammonia can be reacted with the to-be-reacted during each ammonolysis reaction through the feeding device, the first feeding pipe and the second feeding pipe.
  • the molar ratio of the raw materials reaches a maximum value, and the occurrence of side reactions is suppressed, thereby improving the yield of the target product and the conversion rate of the raw materials.
  • the feeding device is used to introduce an ammonia source for the ammonolysis reaction
  • the first feeding pipe is used to supplement the ammonia consumed in the ammonolysis reaction process
  • the second feeding pipe is used to provide ammonia Decompose the raw materials to be reacted required for the reaction.
  • the continuous ammonolysis reaction system further includes an ammonia recovery device, the ammonia recovery device is connected to the flash evaporation device, and the ammonia recovery device is used to recover Ammonia, get recycled ammonia.
  • the ammonia recovery device is also connected to the feed device to deliver the recovered ammonia to the feed device.
  • the continuous ammonolysis reaction system further includes an adjustment device, the adjustment device is connected in series with the nth ammoniating autoclave, the buffer device is connected in series with the adjustment device, and the The adjustment device is a vessel for the ammonolysis reaction.
  • the adjustment device is connected with a first feed pipe.
  • a preparation method of taurine alkali metal salt adopts the above-mentioned continuous ammonolysis reaction system, and the preparation method includes the following steps:
  • the feeding device is used to provide ammonia water to the first ammoniating autoclave, and the first ammoniating autoclave is supplied to the first ammoniating autoclave through the first feeding pipe.
  • n sets of the ammoniating autoclaves provide an ammonia source, and each of the ammoniating autoclaves is provided with an isethionate alkali metal salt solution through the second feed pipe, so that each of the ammoniating autoclaves All carry out the ammonolysis reaction and make the reaction liquid enter the buffer device in a series sequence to obtain a mixed material;
  • the alkali metal isethionate enters the system through the second feed pipe, and the instantaneous concentration of the alkali metal isethionate in the system is low .
  • Make the reaction molar ratio of ammonia and isethionate alkali metal salt reach the maximum value can greatly reduce the production of by-products such as alkali metal salt of ditaurine, and make the yield of alkali metal salt of taurine reach 90 %
  • the conversion rate of alkali metal isethionate exceeds 95%.
  • the process is safe and stable, the product composition is stable, and the reproducibility is high.
  • the volume of ammonia in the ammoniating autoclave is 60%-90% of the volume of the ammoniating autoclave.
  • the ammonia source includes liquid ammonia.
  • the feeding device provides ammonia to the first ammoniated autoclave at a rate of 6.0m 3 /h-10.0m 3 /h, and the first inlet
  • the feed pipe provides ammonia source from the first ammoniated autoclave to the nth ammoniated autoclave at a rate of 0.1m 3 /h-0.2m 3 /h, and the second feed pipe 1.
  • the rate at which the ammoniated autoclave provides the alkali metal isethionate solution is 0.1m 3 /h-0.3m 3 /h.
  • step (2) the second feed pipe provides the isethionate alkali metal salt solution to each of the ammoniated autoclaves by dripping.
  • each of the ammoniated autoclaves is subjected to the ammonolysis reaction, and the reaction liquid enters the adjustment device in a series sequence, and then enters the buffer through the adjustment device. Device to obtain a mixture of materials.
  • step (2) further includes providing an ammonia source to the adjusting device in a continuous or intermittent manner through the first feed pipe.
  • step (5) the ammonia after the depressurization flash vaporization is also recovered by the ammonia recovery device to obtain recovered ammonia.
  • the recovered ammonia is provided to the feeding device.
  • step (2) when step (5) is performed, step (2) is restarted.
  • a preparation method of taurine comprising the preparation method of the alkali metal salt of taurine, and
  • the ammonolysis product prepared by the continuous ammonolysis reaction system of the present application is used to continue the preparation of taurine
  • the ammonolysis product is mainly taurine alkali metal salt, isethionate alkali metal salt, and ditaurine
  • the content of the alkali metal salt and the alkali metal salt of tritaurine is extremely low. Therefore, after the mother liquor is separated, there is no need to recycle the mother liquor, which simplifies the process and makes the process safer, more stable and reliable.
  • it further includes destroying the mother liquor in step (6).
  • Figure 1 is a schematic diagram of the continuous ammonolysis reaction system of the application.
  • FIG. 2 is a schematic diagram of the taurine production process of the application.
  • feeding device 20, high pressure reaction device; 30, buffer device; 40, flashing device; 50, ammonia recovery device; 60, first feeding pipe; 70, second feeding pipe; 80, Acidification device; 90, separation device; 100, mother liquor recovery device; 110, incinerator; 120, crystallization device; 130, adjustment device; 200, ammoniated autoclave.
  • the continuous ammonolysis reaction system is used to carry out the ammonolysis reaction to generate the target product, improve the yield of the target product and the conversion rate of the raw materials to be reacted, and Improve the productivity, safety, stability and reliability of the process.
  • the continuous ammonolysis reaction system includes a high-pressure reaction device 20, a buffer device 30, and a flashing device 40 connected in series in sequence.
  • the high pressure reaction device 20 includes n ammoniating autoclaves 200, the first ammoniating autoclave 200 to the nth ammoniating autoclave 200 are connected in series in sequence, and the ammoniating autoclave 200 is ammonia.
  • a vessel for the hydrolysis reaction in which ammonia is used as the ammoniating agent in the ammonolysis reaction. Therefore, when multiple ammoniating autoclaves 200 connected in series are simultaneously used for the ammonolysis reaction, the pressure, temperature and maintenance time corresponding to the kettle-type batch reaction can be ensured, and the pipeline-type continuous reaction production capacity can be achieved.
  • two or more ammoniating autoclaves 200 can be connected in series to meet the requirements of use, that is, n ⁇ 2.
  • n ⁇ 2 the requirements of use
  • the volume of the ammoniated autoclave is 0.5 m 3 -5 m 3 .
  • the first ammoniating autoclave 200 is connected to the feeding device 10, and the first ammoniating autoclave 200 to the nth ammoniating autoclave 200 are all connected to
  • the first feed pipe 60 is connected with a second feed pipe 70 to each of the ammoniated autoclaves 200.
  • the feeding device 10 is used to introduce an ammonia source for the ammonolysis reaction, such as ammonia water
  • the first feeding pipe 60 is used to supplement the ammonia consumed in the ammonolysis reaction process, such as liquid ammonia
  • the second inlet The feed pipe 70 is used to provide the raw materials to be reacted required for the ammonolysis reaction, such as alkali metal isethionate, etc., so that it can pass through the feed device 10, the first feed pipe 60 and the second feed pipe 70.
  • Precise control makes the molar ratio of ammonia to the raw material to be reacted in each ammonolysis reaction process reach a maximum value, thereby increasing the yield of the target product and the conversion rate of the raw material to be reacted.
  • the buffer device 30 is connected to the n-th ammoniating autoclave 200, and is used to receive the ammoniation reaction in the first to n-th ammoniating autoclaves 200 Mixture of materials.
  • the pressure difference between the first ammoniating autoclave 200 and the n-th ammoniating autoclave 200 is very small. Therefore, the pressure difference between the n-th ammoniating autoclave 200 and the buffer device 30 can be used.
  • the pressure difference caused by the reaction liquid in the ammoniated autoclave 200 flows in a series sequence and enters the buffer device 30. Therefore, the input and output of the ammonification autoclave 200 can be controlled by the buffer device 30 to improve the safety of the continuous ammonolysis reaction system, so that the continuous ammonolysis reaction system of the present application can operate continuously to realize continuous production.
  • the buffer device 30 Since the pressure difference between the n-th ammoniating autoclave 200 and the buffer device 30 will cause the unreacted ammonia source or the incompletely reacted reaction solution to enter the buffer device 30 in advance, the buffer device 30 There is also a discharge pipe to remove the poorly collected mixture.
  • the discharge pipe of the buffer device 30 is opened to remove the poorly collected mixture materials, and then the discharge pipe is closed Re-collection is carried out to obtain a mixture of materials.
  • the flashing device 40 is connected to the buffering device 30 for receiving the mixed material in the buffering device 30 and for flashing to obtain the ammonolysis product.
  • the feed valve of the buffer device 30 is closed, the discharge valve is opened, and the mixture in the buffer device 30 uses the pressure difference to enter the flash vaporizer.
  • the feeding of the ammonification autoclave 200 is stopped to suspend the progress of the ammonolysis reaction.
  • the discharge valve of the buffer device 30 is closed and the feed valve is opened.
  • the feed of the ammoniating autoclave 200 is reopened to restart the ammonolysis reaction. Continue to circulate accordingly to achieve continuous production.
  • the feed valve and the discharge valve of the buffer device 30 may be automatically controlled by an automatic shut-off valve.
  • the continuous ammonolysis reaction system further includes an ammonia recovery device 50, the ammonia recovery device 50 is connected to the flashing device 40, and the ammonia recovery device 50 is used to recover the plant.
  • the ammonia in the flash vaporizer 40 is recovered ammonia, and the recovered ammonia may be liquid ammonia or ammonia water.
  • the ammonia recovery device 50 is also connected to the feed device 10 to transport the recovered ammonia to the feed device 10 for recycling, so as to reduce the additional supplementation and liquidity of ammonia.
  • the use of ammonia reduces production costs.
  • the reaction time of each ammonification autoclave 200 is determined by the number, volume, and flow rate of the raw materials of the ammonification autoclave 200 connected in series.
  • the ammonolysis reaction is continuously carried out, so that the unreacted raw materials to be reacted in the last ammoniated autoclave 200 can be completely reacted in the discharge time, until the raw materials to be reacted in the nth ammoniated autoclave 200 are completely reacted.
  • the reaction is carried out and the material is discharged to the buffer device 30 to obtain a mixed material.
  • the continuous ammonolysis reaction system further includes an adjusting device 130, which is connected in series to the n-th ammoniating autoclave 200, and the buffer device 30 is connected in series to the adjusting device 130.
  • the adjusting device 130 is a container for the ammonolysis reaction, so that the unreacted raw materials to be reacted in the n-th ammoniating autoclave 200 are reacted in the adjusting device 130.
  • the adjusting device 130 is also connected with a first feeding pipe 60 for feeding the adjusting device 130 Replenish the ammonia consumed during the ammonolysis reaction.
  • this application also provides a method for preparing an alkali metal salt of taurine.
  • the preparation method adopts the above-mentioned continuous ammonolysis reaction system, and the preparation method includes the following steps:
  • the feed device 10 supplies ammonia water to the first ammoniated autoclave 200, and sends ammonia water to the first ammoniated autoclave through the first feed pipe 60.
  • the kettle 200 to the n-th ammoniating autoclave 200 provide an ammonia source, and each of the ammoniating autoclave 200 is provided with an isethionate alkali metal salt solution through the second feed pipe 70, so that each One of the ammoniated autoclaves 200 are all subjected to an ammonolysis reaction, and the reaction liquid enters the buffer device 30 in a series sequence to obtain a mixture of materials;
  • the feeding device 10 is stopped to supply ammonia to the first ammoniating autoclave, and the first feeding is stopped.
  • the feed pipe 60 provides an ammonia source to the first ammoniated autoclave 200 to the nth ammoniated autoclave 200, and the second feed pipe 70 is stopped to provide hydroxyl to each of the ammoniated autoclaves 200.
  • Ethyl sulfonic acid alkali metal salt solution, and the mixture material in the buffer device 30 enters the flash device 40;
  • the mixture material in the flashing device 40 is flashed under pressure reduction to obtain an ammonolysis product, and the ammonolysis product includes an alkali metal salt of taurine.
  • step (1) the ammonia water is obtained by configuring at least two of liquid ammonia, ammonia water, and water in the feeding device 10, and the mass concentration of ammonia is 25%-50%.
  • the feeding device 10 provides ammonia water to the first ammoniating autoclave 200 so that each ammoniating autoclave 200 is filled with ammonia water.
  • the volume of ammonia in the ammoniating autoclave 200 is 60%-90% of the volume of the ammoniating autoclave 200.
  • step (2) the reaction temperature is 250° C. to 290° C.
  • the reaction pressure is 14 MPa to 24 MPa
  • the rotation speed of each ammoniating autoclave 200 is 100 r/min to 500 r/min.
  • the ammonia source provided by the first feed pipe 60 to the first to the nth ammoniating autoclave 200 to the nth ammoniating autoclave 200 is preferably liquid ammonia. Because the alkali metal isethionate consumes ammonia during the ammonolysis, if ammonia is added to the first feed pipe 60, the reaction volume in the ammonification autoclave 200 will increase.
  • the isethionate alkali metal salt solution provided by the second feed pipe 70 to each ammoniating autoclave 200 includes sodium isethionate solution, potassium isethionate solution, and lithium isethionate solution. At least one is preferably a sodium isethionate solution, and the mass concentration of the alkali metal isethionate in the alkali metal isethionate solution is 30%-60%.
  • the feeding device 10 supplies ammonia to the first ammoniated autoclave 200 at a rate of 6.0m 3 /h-10.0m 3 /h, and the first feeding pipe 60 supplies ammonia to the first ammoniated autoclave 200.
  • the speed at which the autoclave 200 to the n-th ammoniated autoclave 200 provides ammonia source is 0.1m 3 /h-0.2m 3 /h, and the second feed pipe 70 supplies each ammoniated autoclave
  • the rate at which 200 provides isethionine alkali metal salt solution is 0.1m 3 /h-0.3m 3 /h.
  • the second feed pipe 70 provides the alkali metal isethionate solution to each of the ammoniated autoclaves 200 by dripping, and the first feed pipe 60
  • the method of supplying the ammonia source to the first ammoniating autoclave 200 to the nth ammoniating autoclave 200 may also be dropwise addition.
  • the preparation method can accurately control the feeding speed of the feeding device 10, the first feeding pipe 60, and the second feeding pipe 70, so that the ammonia and hydroxyethyl sulfonate in each ammoniating autoclave can be controlled accurately.
  • the molar ratio of acid-alkali metal salt reaches a maximum value, which greatly reduces the production of by-products such as alkali metal salt of ditaurine, so that the yield of alkali metal salt of taurine can reach more than 90%.
  • the conversion rate of the metal salt exceeds 95%.
  • the process is safe and stable, the product composition is stable, and the reproducibility is high.
  • the contents of the ammoniating autoclave 200 can be adjusted.
  • the residence time of the reaction solution is controlled.
  • the speed at which the first feed pipe 60 and the second feed pipe 70 supply liquid ammonia and the alkali metal isethionate solution to each ammoniating autoclave 200 can be the same or different of.
  • the second feed pipe 70 can be used to provide isethionate to each of the ammoniating autoclaves 200 The speed of the alkali metal salt solution remains the same.
  • the nth ammoniating autoclave 200 can be reduced.
  • the adjusting device 130 when the continuous ammonolysis reaction system includes the adjusting device 130, the adjusting device 130 will also be filled with ammonia during the feeding process of step (1), so that each of the ammoniated components can be made in step (2).
  • the reaction liquid in the autoclave 200 enters the adjusting device 130 in a serial sequence, so that the incompletely reacted alkali metal isethionate in the reaction liquid reacts completely in the adjusting device 130, and then passes through the adjusting device 130. 130 enters the buffer device 30 to obtain a mixture material.
  • step (2) an ammonia source is also provided to the adjusting device 130 through the first feed pipe 60 in a continuous or intermittent manner to supplement the ammonia consumed by the ammonolysis reaction.
  • step (2) after the ammonolysis reaction in the ammonification autoclave 200 has been carried out for a certain period of time or after the ammonolysis reaction has stabilized, it may also include opening the discharge pipe of the buffer device 30 to remove the poorly collected mixture materials, and then Close the discharge pipe for re-collection to obtain a better quality mixture.
  • the ammonia recovery device 50 is also used to recover the reduced-pressure flashed ammonia to obtain recovered ammonia.
  • the recovered ammonia may be ammonia or liquid ammonia.
  • water circulation is used to recover the ammonia after the depressurization and flash evaporation to obtain ammonia water.
  • the recovered ammonia is provided to the feeding device 10 for recycling, so as to reduce the use of liquid ammonia in the feeding device 10 and reduce production costs.
  • step (2) Since the feeding device 10 is supplemented with ammonia in step (2) and the first feeding pipe 60 is supplemented with liquid ammonia in step (2), it is possible to maintain each ammoniating autoclave 200 during the ammonolysis reaction.
  • the volume of the reaction solution in the process Therefore, referring to the specific use of the continuous ammonolysis reaction system, when step (5) is performed, step (2) can be restarted and cycled in order to realize the continuous production of the alkali metal salt of taurine.
  • this application also provides a method for preparing taurine, including the method for preparing the alkali metal salt of taurine, and
  • step (6) specifically, sulfuric acid, hydrochloric acid, etc. may be used to acidify the ammonolysis product in the acidification device 80 to obtain a solid-liquid acidification product, which is separated by the separation device 90 to obtain a solid product and mother liquor.
  • ammonolysis products prepared by the continuous ammonolysis reaction system of the present application are mainly taurine alkali metal salt, isethionate alkali metal salt, ditaurine alkali metal salt and tritaurine alkali metal salt
  • the salt content is extremely low. Therefore, after the solid product is separated, the mother liquor described in step (6) can be directly destroyed without recycling the mother liquor. This not only simplifies the process, but also avoids the stability problems and safety caused by the mother liquor. Hidden dangers make the production process safer, more stable and reliable.
  • the mother liquor recovery device 100 is used to recover the mother liquor separated by the separation device 90 and transported to the incinerator 110 for incineration.
  • step (7) the solid product can be specifically cooled and crystallized in the crystallization device 120 to obtain a crude taurine, and the crude taurine is purified to obtain a pure taurine.
  • the continuous ammonolysis reaction systems of the following examples all use 6 sets of 5.0m 3 ammonification autoclaves connected in series.
  • the ammonification autoclaves in series are all in the form of upper feeding and bottom discharging of the bottom pipe, and high-pressure pipes are used. Connect to each other.
  • Use a high-pressure pump and a feeding device to press ammonia into the first ammoniated autoclave use the first feed pipe to drop liquid ammonia into the first to sixth ammoniated autoclaves, and use the high-pressure pump and the second inlet
  • the feed pipe drips sodium isethionate aqueous solution into the first to sixth ammoniated autoclaves.
  • the pressure difference between the first to the sixth ammoniating autoclave in series is very small.
  • the pressure difference generated by the discharge of the sixth ammoniating autoclave is used to buffer the reaction liquid in the ammoniating autoclave in the sequence of the series.
  • the device flows.
  • Liquid ammonia and water are used to prepare a 40% aqueous ammonia solution, and sodium isethionate solid and water are used to prepare a 40% sodium isethionate aqueous solution.
  • the prepared ammonia water with a concentration of 40% is pressed into the first ammoniating autoclave through the high-pressure pump and the feeding device, so that the ammonia water in the first to sixth ammoniating autoclaves in series reaches the volume of the ammoniation autoclave. When 80% of the feed is reached, stop feeding.
  • the flow rate of ammonia water in the feeding device is 10.0m 3 /h, and the flow rate of liquid ammonia in the first feeding pipe is 0.10m 3 /h.
  • the flow rate of the sodium isethionate aqueous solution in the second feed pipe is 0.22m 3 /h.
  • the reaction liquid in the first to the sixth ammoniated autoclave flows in series, passes through the feed valve of the buffer device and enters the buffer device, and the buffer device collects the mixed material.
  • the pressure of the buffer device reaches 14.5MPa, it balances with the pressure of the sixth ammoniating autoclave, close the feed valve of the buffer device, open the discharge valve of the buffer device, and pressure the mixture into the flash vaporizer.
  • the pressure of the buffer device and the flashing device is balanced, close the discharge valve of the buffer device, open the feed valve of the buffer device, and make the feeding device, the first feeding pipe and the second feeding pipe into the ammoniating autoclave Re-feeding is carried out, and the cycle continues accordingly.
  • the mixture material in the flashing device is flashed by pressure reduction to obtain an ammonolysis product, and the excess ammonia in it is recycled to the ammonia recovery device using water recycling, and the formed ammonia water is recycled to the feeding device for continued use. After the system has been running continuously for 8 hours, samples are taken for analysis and calculations. The results are shown in Table 1.
  • the solid product is transferred to a crystallization device, and the temperature is lowered and crystallized to obtain a crude taurine.
  • the crude taurine is purified to obtain a pure taurine.
  • the mother liquor is recovered by the mother liquor recovery device and then enters the incineration plant for incineration treatment, and the mother liquor is not reused.
  • the pure taurine product is analyzed, and the taurine content in the pure taurine product is 99.96%, the content of sodium isethionate is 0.02%, sodium ditaurate and sodium tritaurate Not detected, the content of other impurities is 0.02%.
  • Liquid ammonia and water are used to prepare 40% ammonia water, and sodium isethionate solid and water are used to prepare 50% sodium isethionate aqueous solution.
  • the prepared ammonia water with a concentration of 40% is pressed into the first ammoniating autoclave through the high-pressure pump and the feeding device, so that the ammonia water in the first to sixth ammoniating autoclaves in series reaches the volume of the ammoniation autoclave. When 80% of the feed is reached, stop feeding.
  • the stirring device to make the first to sixth ammoniating autoclaves reach 300r/min, start to heat up the first to sixth ammoniating autoclaves, and use the discharge valve to control the ammoniated autoclave in the system pressure.
  • 40% ammonia water is added to the first ammoniating autoclave through the high-pressure pump and the feeding device, and the high-pressure pump and The second feed pipe drips 50% sodium isethionate aqueous solution into the first to sixth ammoniated autoclaves to carry out the ammonolysis reaction, and at the same time passes the first feed pipe to the first to sixth ammonia Liquid ammonia was added dropwise to the autoclave to supplement the ammonia consumed in the reaction process.
  • the flow rate of ammonia in the feeding device was 8.0m 3 /h, and the flow rate of liquid ammonia in the first feeding pipe was 0.1m 3 /h.
  • the flow rate of the sodium isethionate aqueous solution in the second feed pipe is 0.11 m 3 /h.
  • the reaction liquid in the first to the sixth ammoniated autoclave flows in a series sequence, passes through the feed valve of the buffer device and enters the buffer device, and the buffer device collects the mixed material.
  • the pressure of the buffer device reaches 18.3 MPa, it balances with the pressure of the sixth ammoniating autoclave, close the feed valve of the buffer device, open the discharge valve of the buffer device, and pressure the mixture into the flash vaporizer.
  • the pressure of the buffer device and the flashing device is balanced, close the discharge valve of the buffer device, open the feed valve of the buffer device, and make the feeding device, the first feeding pipe and the second feeding pipe into the ammoniating autoclave Re-feeding is carried out, and the cycle continues accordingly.
  • the mixture material in the flashing device is flashed by pressure reduction to obtain the ammonolysis product, and the excess ammonia in it is recovered by water recycling to the ammonia recovery device, and the formed ammonia water is recycled to the feeding device for continued use. After the system has been running continuously for 8 hours, samples are taken for analysis and calculations. The results are shown in Table 2.
  • the solid product is transferred to a crystallization device, and the temperature is lowered and crystallized to obtain a crude taurine.
  • the crude taurine is purified to obtain a pure taurine.
  • the mother liquor is recovered by the mother liquor recovery device and then enters the incineration plant for incineration treatment, and the mother liquor is not reused.
  • the pure taurine product was analyzed, and the content of taurine in the pure taurine product was 99.91%, the content of sodium isethionate was 0.02%, sodium ditaurate and sodium tritaurate Not detected, the content of other impurities is 0.07%.
  • Liquid ammonia and water are used to prepare 50% ammonia water, and sodium isethionate solid and water are used to prepare 50% sodium isethionate aqueous solution.
  • the prepared ammonia water with a concentration of 50% is pressed into the first ammoniating autoclave through the high-pressure pump and the feeding device, so that the ammonia water in the first to sixth ammoniating autoclaves in series reaches the volume of the ammoniated autoclave. When 80% of the feed is reached, stop feeding.
  • the flow rate of ammonia in the feeding device was 9.0m 3 /h
  • the flow rate of liquid ammonia in the first feeding pipe was 0.1m 3 /h
  • the flow rate of the sodium isethionate aqueous solution in the second feed pipe is 0.11 m 3 /h.
  • the reaction liquid in the first to the sixth ammoniated autoclave flows in series, passes through the feed valve of the buffer device and enters the buffer device, and the buffer device collects the mixed material.
  • the pressure of the buffer device reaches 18.6MPa, it balances with the pressure of the sixth ammoniating autoclave, close the feed valve of the buffer device, open the discharge valve of the buffer device, and pressure the mixture into the flashing device.
  • the pressure of the buffer device and the flashing device is balanced, close the discharge valve of the buffer device, open the feed valve of the buffer device, and make the feeding device, the first feeding pipe and the second feeding pipe into the ammoniating autoclave Re-feeding is carried out, and the cycle continues accordingly.
  • the mixture material in the flashing device is flashed by pressure reduction to obtain an ammonolysis product, and the excess ammonia in it is recycled to the ammonia recovery device using water recycling, and the formed ammonia water is recycled to the feeding device for continued use.
  • samples are taken for analysis and calculations. The results are shown in Table 3.
  • the flashed ammonolysis product is transferred to an acidification device, and concentrated H 2 SO 4 is added dropwise for acidification, until the pH is 7.0, the dropwise addition of concentrated H 2 SO 4 is stopped, and a solid-liquid acidification product is obtained.
  • the acidification product is separated by a separation device, the solid product is transferred to a crystallization device, and the temperature is lowered and crystallized to obtain a crude taurine.
  • the crude taurine is purified to obtain a pure taurine.
  • the mother liquor is recovered by the mother liquor recovery device and then enters the incineration plant for incineration treatment, and the mother liquor is not reused.
  • the pure taurine product was analyzed, and the content of taurine in the pure taurine product was 99.92%, the content of sodium isethionate was 0.02%, sodium ditaurate and sodium tritaurate Not detected, the content of other impurities is 0.06%.
  • Liquid ammonia and water are used to prepare 50% ammonia water, and sodium isethionate solid and water are used to prepare 45% sodium isethionate aqueous solution.
  • the prepared ammonia water with a concentration of 50% is pressed into the first ammoniating autoclave through the high-pressure pump and the feeding device, so that the ammonia water in the first to sixth ammoniating autoclaves in series reaches the volume of the ammoniated autoclave. When 80% of the feed is reached, stop feeding.
  • the flow rate of ammonia in the feeding device is 8.0m 3 /h
  • the flow rate of liquid ammonia in the first feeding pipe is 0.1m 3 /h
  • the flow rate of the sodium isethionate aqueous solution in the second feed pipe is 0.18 m 3 /h.
  • the reaction liquid in the first to the sixth ammoniated autoclave flows in series, passes through the feed valve of the buffer device and enters the buffer device, and the buffer device collects the mixed material.
  • the pressure of the buffer device reaches 19.2MPa, it balances with the pressure of the sixth ammoniating autoclave, close the feed valve of the buffer device, open the discharge valve of the buffer device, and pressure the mixture into the flashing device.
  • the pressure of the buffer device and the flashing device is balanced, close the discharge valve of the buffer device, open the feed valve of the buffer device, and make the feeding device, the first feeding pipe and the second feeding pipe into the ammoniating autoclave Re-feeding is carried out, and the cycle continues accordingly.
  • the mixture material in the flashing device is flashed by pressure reduction to obtain an ammonolysis product, and the excess ammonia in it is recycled to the ammonia recovery device using water recycling, and the formed ammonia water is recycled to the feeding device for continued use. After the system has been running continuously for 8 hours, samples are taken for analysis and calculations. The results are shown in Table 4.
  • the flashed ammonolysis product is transferred to an acidification device, and concentrated H 2 SO 4 is added dropwise for acidification, until the pH is 7.0, the dropwise addition of concentrated H 2 SO 4 is stopped, and a solid-liquid acidification product is obtained.
  • the acidified product is separated by a separation device, the solid product is transferred to a crystallization device, and the temperature is lowered and crystallized to obtain a crude taurine, and the crude taurine is purified to obtain a pure taurine.
  • the mother liquor is recovered by the mother liquor recovery device and then enters the incineration plant for incineration treatment, and the mother liquor is not reused.
  • the pure taurine product is analyzed, and the taurine content in the pure taurine product is 99.90%, the content of sodium isethionate is 0.02%, sodium ditaurate and sodium tritaurate Not detected, the content of other impurities is 0.08%.
  • Liquid ammonia and water are used to prepare 50% ammonia water, and sodium isethionate solid and water are used to prepare 45% sodium isethionate aqueous solution.
  • the prepared ammonia water with a concentration of 50% is pressed into the first ammoniating autoclave through the high-pressure pump and the feeding device, so that the ammonia water in the first to sixth ammoniating autoclaves in series reaches the volume of the ammoniated autoclave. When 80% of the feed is reached, stop feeding.
  • the flow rate of ammonia in the feeding device was 8.0m 3 /h, and the flow rate of liquid ammonia in the first feeding pipe was 0.1m 3 /h.
  • two feed conduit a flow rate of an aqueous solution of sodium isethionate were 0.22m 3 /h,0.20m 3 /h,0.18m 3 /h,0.16m 3 /h,0.14m 3 / h.
  • the reaction liquid in the first to the sixth ammoniated autoclave flows in series, passes through the feed valve of the buffer device and enters the buffer device, and the buffer device collects the mixed material.
  • the pressure of the buffer device reaches 18.4MPa, it balances with the pressure of the sixth ammoniating autoclave, close the feed valve of the buffer device, open the discharge valve of the buffer device, and pressure the mixture into the flashing device.
  • the pressure of the buffer device and the flashing device is balanced, close the discharge valve of the buffer device, open the feed valve of the buffer device, and make the feeding device, the first feeding pipe and the second feeding pipe into the ammoniating autoclave Re-feeding is carried out, and the cycle continues accordingly.
  • the mixture material in the flashing device is flashed by pressure reduction to obtain an ammonolysis product, and the excess ammonia in it is recycled to the ammonia recovery device using water recycling, and the formed ammonia water is recycled to the feeding device for continued use.
  • samples are taken for analysis and calculations. The results are shown in Table 5.
  • the flashed ammonolysis product is transferred to an acidification device, and concentrated H 2 SO 4 is added dropwise for acidification, until the pH is 7.0, the dropwise addition of concentrated H 2 SO 4 is stopped, and a solid-liquid acidification product is obtained.
  • the acidification product is separated by a separation device, the solid product is transferred to a crystallization device, and the temperature is lowered and crystallized to obtain a crude taurine.
  • the crude taurine is purified to obtain a pure taurine.
  • the mother liquor is recovered by the mother liquor recovery device and then enters the incineration plant for incineration treatment, and the mother liquor is not reused.
  • the pure taurine product is analyzed, and the taurine content in the pure taurine product is 99.90%, the content of sodium isethionate is 0.02%, sodium ditaurate and sodium tritaurate Not detected, the content of other impurities is 0.08%.
  • the metered sodium isethionate solid is dissolved in an autoclave containing a certain concentration of ammonia water (25%-50%), and reacted at 250°C-290°C, 14MPa-25MPa Under the conditions, the ammoniating reaction is carried out for 1 hour to 3 hours to obtain an aqueous solution of sodium taurate. According to calculation, the yield of sodium taurate is 77%-80% on average.
  • the yield of sodium taurate in the preparation method of the present application is about 95%, which is far greater than the 77%-80% yield of the batch kettle type. It can be seen that in the preparation process of taurine, firstly, the content of sodium isethionate, sodium ditaurate and sodium tritaurate is less, which is beneficial to acidification, crystallization and purification in the later stage, and the obtained cattle The sulfonic acid content is close to 100%. Secondly, it can avoid the complicated mother liquor application process, simplify the production process, and improve the safety, stability and reliability of the production process.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne un système de réaction d'ammonolyse continue et un procédé de préparation de sel de taurine-métal alcalin et de taurine à l'aide du système de réaction d'ammonolyse continue. Le système de réaction d'ammonolyse continue comprend un dispositif de réaction haute pression, le dispositif de réaction haute pression comprend n autoclaves d'ammoniation, n≥2, le premier autoclave d'ammoniation et le nième autoclave d'ammoniation sont reliés séquentiellement en série, l'autoclave d'ammoniation est une cuve destinée à la réaction d'ammonolyse, la réaction d'ammonolyse met en œuvre de l'ammoniac comme agent d'ammoniation, le premier autoclave d'ammoniation est relié à un dispositif d'apport, les autoclaves du premier autoclave d'ammoniation au nième autoclave d'ammoniation sont tous reliés à un premier tuyau d'apport, chaque autoclave d'ammoniation est relié à un second tuyau d'apport ; un dispositif de stockage intermédiaire, le dispositif de stockage intermédiaire est relié au nième autoclave d'ammoniation, qui est destiné à recevoir les matériaux mélangés suite à la réaction d'ammonolyse survenant du premier autoclave d'ammoniation au nième autoclave d'ammoniation ; un dispositif de vaporisation instantanée, le dispositif de vaporisation instantanée étant relié au dispositif de stockage intermédiaire, qui est destiné à recevoir les matériaux mélangés dans le dispositif de stockage intermédiaire et à obtenir le produit d'ammonolyse par vaporisation instantanée.
PCT/CN2020/112059 2019-12-27 2020-08-28 Système de réaction d'ammonolyse continue, procédé de préparation de sel de taurine-métal alcalin et de taurine Ceased WO2021128917A1 (fr)

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