WO2021128917A1 - Continuous ammonolysis reaction system, preparation method for taurine alkali metal salt and taurine - Google Patents

Continuous ammonolysis reaction system, preparation method for taurine alkali metal salt and 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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PCT/CN2020/112059
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French (fr)
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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浙江新和成药业有限公司
上虞新和成生物化工有限公司
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02Preparation 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
    • C07C303/04Preparation 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
    • C07C303/06Preparation 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02Preparation 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/32Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/42Separation; Purification; Stabilisation; Use of additives
    • C07C303/44Separation; Purification
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01Sulfonic acids
    • C07C309/02Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/13Sulfonic 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
    • C07C309/14Sulfonic 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.

Abstract

Provided are a continuous ammonolysis reaction system, and a method for preparing taurine alkali metal salt and taurine using the continuous ammonolysis reaction system. The continuous ammonolysis reaction system comprises a high-pressure reaction device, the high-pressure reaction device comprises n ammoniating autoclaves, n≥2, the first ammoniating autoclave to the nth ammoniating autoclave are connected in series in sequence, the ammoniating autoclave is a vessel for the ammonolysis reaction, 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 autoclave are all connected with a first feed pipe, each ammoniating autoclave is connected with a second feed pipe; a buffer device, the buffer device is connected with the nth ammoniating autoclave, which is used to receive the mixed materials after the ammonolysis reaction in the first ammoniating autoclave to the nth ammoniating autoclave; a flashing device, the flashing device is connected with the buffer device, which is used to receive the mixed materials in the buffer device and obtain the ammonolysis product by means of flashing.

Description

连续式氨解反应系统、牛磺酸碱金属盐及牛磺酸的制备方法Continuous ammonolysis reaction system, taurine alkali metal salt and preparation method of taurine
相关申请Related application
本申请要求2019年12月27日申请的,申请号为201911380161.7,发明名称为“连续式氨解反应系统、牛磺酸碱金属盐及牛磺酸的制备方法”的中国专利申请的优先权,其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed on December 27, 2019, the application number is 201911380161.7, and the invention title is "Continuous Ammoniolysis Reaction System, Taurine Alkali Metal Salt and Preparation Method of Taurine", The entire content is incorporated into this application by reference.
技术领域Technical field
本申请涉及牛磺酸技术领域,特别是涉及连续式氨解反应系统、牛磺酸碱金属盐及牛磺酸的制备方法。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.
背景技术Background technique
牛磺酸又称β-氨基乙磺酸,是一种含硫的非蛋白氨基酸,广泛应用于医药、食品添加剂、荧光增白剂、有机合成等领域,制备方法包括环氧乙烷法、牛磺酸铵法、一乙醇胺法和乙醇法等。Taurine, also known as β-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.
其中,环氧乙烷法是当前牛磺酸的主要制备方法,而环氧乙烷法中,研究最多的是氨解反应,主要是因为:第一、羟乙基磺酸钠在高温高压的反应体系下进行氨解反应时容易产生二牛磺酸钠等副产物,严重影响目标产物牛磺酸钠的收率和羟乙基磺酸钠的转化率;第二、二牛磺酸钠等副产物和残留的羟乙基磺酸钠,由于在水中溶解度较大,经酸化、分离工艺后大多仍留在母液中,如何处理母液中的羟乙基磺酸钠、二牛磺酸钠等副产物、硫酸钠成为棘手的问题。Among them, 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. When carrying out the ammonolysis reaction in the reaction system, it is easy to produce 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.
氨解反应方程式:Ammonialysis reaction equation:
主反应
Figure PCTCN2020112059-appb-000001
Main reaction
Figure PCTCN2020112059-appb-000001
副反应
Figure PCTCN2020112059-appb-000002
side effects
Figure PCTCN2020112059-appb-000002
间歇釜式工艺是当前较普遍采用的工业化氨解操作方式,该方法技术成熟可靠,运行稳定,反应收率在77%-80%左右。但存在的其不足之处是:1、为保证牛磺酸钠收率和选择性,反应体系中氨要远远过量,使投入氨化釜内的羟乙基磺酸钠与氨,二者摩尔比在1:(10-30)之间。2、随着氨化反应的进行,物料中氨和羟乙基磺酸钠的浓度逐渐减少,反应推动力变小,需要维持较长的反应时间,降低了生产效率。3、间歇釜式工艺单批次产量低、生产周期长。 且间歇式生产,能耗高、效率低,设备产能小,回收氨量大、氨耗高。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%. However, its shortcomings are: 1. In order to ensure the yield and selectivity of sodium taurate, 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). 2. With the progress of the amination reaction, 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. 3. 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.
传统技术中也有将高压反应釜间歇操作生产方法改造为管道化连续操作,如朱圣东在《化工科技》2001年第9卷第3期中公开了牛磺酸氨化反应管道化技术,该工艺是将25%的氨水溶液与35%的羟基磺酸钠水溶液及少量的催化剂混合后,由贮罐经高压耐蚀泵加压到18MPa-20MPa,然后经预热器升温至280℃,进入管式反应器,在管式反应器内反应30min,反应后的物料连续流出,降压、闪蒸处理得到氨解产物。管道化连续操作具有生产能力强、工艺周期短、良好的稳定性等特点,但该方法操作条件苛刻,设备不仅要承受较高的操作温度,而且要承受流体的高压载荷,还伴有氨水等腐蚀介质的冲刷。同时,由于反应停留时间短,使压力、温度反应过高,物料结焦严重。另外,系统热利用率低,前期要将物料升温至100-200℃再进行反应,反应释放热需要移出。The traditional technology also transforms the production method of high-pressure reactor batch operation into pipelined continuous operation. For example, 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℃ 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. However, the operating conditions of this method are harsh. 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. At the same time, due to the short residence time of the reaction, the pressure and temperature are too high, and the coking of the material is serious. In addition, 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.
发明内容Summary of the invention
根据本申请的各种实施例,提供一种连续式氨解反应系统、牛磺酸碱金属盐及牛磺酸的制备方法。该连续式氨解反应系统,包括:According to various embodiments of the present application, a continuous ammonolysis reaction system, an alkali metal salt of taurine, and a preparation method of taurine are provided. The continuous ammonolysis reaction system includes:
高压反应装置,所述高压反应装置包括n台氨化高压釜,n≥2,第1台所述氨化高压釜至第n台所述氨化高压釜依次串联,所述氨化高压釜为氨解反应的容器,所述氨解反应采用氨作为氨化剂,第1台所述氨化高压釜连接有进料装置,第1台所述氨化高压釜至第n台所述氨化高压釜均连接有第一进料管,每一所述氨化高压釜均连接有第二进料管;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;
缓冲装置,所述缓冲装置与第n台所述氨化高压釜连接,用于接收第1台至第n台所述氨化高压釜中氨解反应后的混合物料;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;
闪蒸装置,所述闪蒸装置与所述缓冲装置连接,用于接收所述缓冲装置中的所述混合物料并通过闪蒸得到氨解产物。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.
上述连续式氨解反应系统中,将用于间歇反应的多台氨化高压釜进行串联,多台氨化高压釜同时用于氨解反应时,既能保证与釜式间歇反应相应的压力、温度及停留时间,又能达到管道式连续反应的产能。而且,上述连续式氨解反应系统中,进料装置用于加料和开始反应,第一进料管用于补充氨解反应过程中消耗的氨,第二进料管用于向氨化高压釜提供氨解反应中的待反应原料,如羟乙基磺酸碱金属盐等,从而,可以通过进料装置、第一进料管和第二进料管使每一氨解反应过程中氨与待反应原料的摩尔比达到极大值,抑制副反应的发生,进而能够提高目标产品的收率和原料的转化率。In the above continuous ammonolysis reaction system, multiple ammonification autoclaves used for batch reactions are connected in series, and when multiple ammonification autoclaves are used for the ammonolysis reaction at the same time, the pressure and pressure corresponding to the kettle-type batch reaction can be ensured. The temperature and residence time can reach the capacity of pipeline continuous reaction. Moreover, in the above-mentioned continuous ammonolysis reaction system, the feeding device is used for feeding and starting the reaction, the first feeding pipe is used to supplement the ammonia consumed in the ammonolysis reaction process, and the second feeding pipe is used to provide ammonia to the ammonification autoclave. 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.
在其中一个实施例中,所述进料装置用于引入氨解反应的氨源,所述第一进料管用于 补充氨解反应过程中消耗的氨,所述第二进料管用于提供氨解反应所需的待反应原料。In one of the embodiments, 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, and the second feeding pipe is used to provide ammonia Decompose the raw materials to be reacted required for the reaction.
在其中一个实施例中,所述连续式氨解反应系统还包括有氨回收装置,所述氨回收装置与所述闪蒸装置连接,所述氨回收装置用于回收所述闪蒸装置中的氨,得到回收氨。In one of the embodiments, 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.
在其中一个实施例中,所述氨回收装置还与所述进料装置连接,以将所述回收氨输送至所述进料装置。In one of the embodiments, the ammonia recovery device is also connected to the feed device to deliver the recovered ammonia to the feed device.
在其中一个实施例中,所述连续式氨解反应系统还包括有调整装置,所述调整装置串联于第n台所述氨化高压釜,所述缓冲装置串联于所述调整装置,所述调整装置为氨解反应的容器。In one of the embodiments, 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.
在其中一个实施例中,所述调整装置连接有第一进料管。In one of the embodiments, the adjustment device is connected with a first feed pipe.
一种牛磺酸碱金属盐的制备方法,所述制备方法采用上述的连续式氨解反应系统,所述制备方法包括以下步骤:A preparation method of taurine alkali metal salt, the preparation method adopts the above-mentioned continuous ammonolysis reaction system, and the preparation method includes the following steps:
(1)通过所述进料装置向第1台所述氨化高压釜中提供氨水,以使串联的每一所述氨化高压釜均充有氨水;(1) Provide ammonia water to the first ammoniating autoclave through the feeding device, so that each ammoniating autoclave connected in series is filled with ammonia water;
(2)在反应温度和反应压力下,通过所述进料装置向第1台所述氨化高压釜提供氨水,通过所述第一进料管向第1台所述氨化高压釜至第n台所述氨化高压釜提供氨源,通过所述第二进料管向每一所述氨化高压釜提供羟乙基磺酸碱金属盐溶液,以使每一所述氨化高压釜均进行氨解反应并使反应液以串联的顺序进入所述缓冲装置中,得到混合物料;(2) Under the reaction temperature and reaction pressure, 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;
(3)所述缓冲装置与第n台所述氨化高压釜的压力平衡后,停止所述进料装置向第1台所述氨化高压釜提供氨水,停止所述第一进料管向第1台所述氨化高压釜至第n台所述氨化高压釜提供氨源,停止所述第二进料管向每一所述氨化高压釜提供羟乙基磺酸碱金属盐溶液,并使所述缓冲装置中的混合物料进入所述闪蒸装置中;(3) After the pressure of the buffer device and the n-th ammoniating autoclave is balanced, stop the feeding device to provide ammonia to the first ammoniating autoclave, and stop the first feeding pipe to supply ammonia to the first ammoniating autoclave. The first ammoniating autoclave to the nth ammoniating autoclave provide ammonia source, and the second feed pipe is stopped to provide alkali metal isethionate solution to each of the ammoniating autoclaves , And make the mixture material in the buffer device enter the flash evaporation device;
(4)所述闪蒸装置与所述缓冲装置的压力平衡后,使所述缓冲装置中的混合物料停止进入所述闪蒸装置中;(4) After the pressures of the flashing device and the buffering device are balanced, stop the mixed material in the buffering device from entering the flashing device;
(5)将所述闪蒸装置中的混合物料降压闪蒸,得到氨解产物,所述氨解产物包括牛磺酸碱金属盐。(5) Depressurizing and flashing the mixture in the flashing device to obtain an ammonolysis product, and the ammonolysis product includes an alkali metal salt of taurine.
使用本申请的连续式氨解反应系统制备牛磺酸碱金属盐时,羟乙基磺酸碱金属盐通过第二进料管进入系统,系统中羟乙基磺酸碱金属盐的瞬时浓度低,使氨与羟乙基磺酸碱金属盐的反应摩尔比达到极大值,可大幅度降低二牛磺酸碱金属盐等副产物的产生,使牛磺酸碱金属盐的收率达到90%以上,羟乙基磺酸碱金属盐的转化率超过95%。而且,工艺安全稳定, 产品组成成分稳定,再现性高。When the continuous ammonolysis reaction system of the present application is used to prepare the alkali metal salt of taurine, 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 % Above, the conversion rate of alkali metal isethionate exceeds 95%. Moreover, the process is safe and stable, the product composition is stable, and the reproducibility is high.
在其中一个实施例中,步骤(1)中,所述氨化高压釜中氨水的体积为所述氨化高压釜的体积的60%-90%。In one of the embodiments, in step (1), the volume of ammonia in the ammoniating autoclave is 60%-90% of the volume of the ammoniating autoclave.
在其中一个实施例中,步骤(2)中,所述氨源包括液氨。In one of the embodiments, in step (2), the ammonia source includes liquid ammonia.
在其中一个实施例中,步骤(2)中,所述进料装置向第1台所述氨化高压釜提供氨水的速度为6.0m 3/h-10.0m 3/h,所述第一进料管向第1台所述氨化高压釜至第n台所述氨化高压釜提供氨源的速度均为0.1m 3/h-0.2m 3/h,所述第二进料管向每一所述氨化高压釜提供羟乙基磺酸碱金属盐溶液的速度均为0.1m 3/h-0.3m 3/h。 In one of the embodiments, in step (2), 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.
在其中一个实施例中,步骤(2)中,所述第二进料管向每一所述氨化高压釜提供羟乙基磺酸碱金属盐溶液的方式为滴加。In one of the embodiments, in step (2), the second feed pipe provides the isethionate alkali metal salt solution to each of the ammoniated autoclaves by dripping.
在其中一个实施例中,步骤(2)中,每一所述氨化高压釜均进行氨解反应并使反应液以串联的顺序进入所述调整装置,再通过所述调整装置进入所述缓冲装置,得到混合物料。In one of the embodiments, in step (2), 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.
在其中一个实施例中,步骤(2)中,还包括通过所述第一进料管以连续式或者间歇式的方式向所述调整装置提供氨源。In one of the embodiments, step (2) further includes providing an ammonia source to the adjusting device in a continuous or intermittent manner through the first feed pipe.
在其中一个实施例中,步骤(5)中,还通过所述氨回收装置回收降压闪蒸后的氨,得到回收氨。In one of the embodiments, in step (5), the ammonia after the depressurization flash vaporization is also recovered by the ammonia recovery device to obtain recovered ammonia.
在其中一个实施例中,所述回收氨提供至所述进料装置。In one of the embodiments, the recovered ammonia is provided to the feeding device.
在其中一个实施例中,在进行步骤(5)时,重新开始步骤(2)。In one of the embodiments, when step (5) is performed, step (2) is restarted.
一种牛磺酸的制备方法,所述制备方法包括所述牛磺酸碱金属盐的制备方法,以及A preparation method of taurine, the preparation method comprising the preparation method of the alkali metal salt of taurine, and
(6)将所述氨解产物进行酸化,分离,得到固体产物和母液;(6) Acidifying and separating the ammonolysis product to obtain a solid product and mother liquor;
(7)将所述固体产物结晶,得到牛磺酸。(7) Crystallize the solid product to obtain taurine.
将使用本申请的连续式氨解反应系统制备得到的氨解产物继续制备牛磺酸时,氨解产物中主要为牛磺酸碱金属盐,羟乙基磺酸碱金属盐、二牛磺酸碱金属盐和三牛磺酸碱金属盐含量极低,所以,分离得到母液后可以不用对母液进行循环套用,简化了工艺,进而使工艺更加安全、稳定、可靠。When 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.
在其中一个实施例中,还包括销毁步骤(6)中所述母液。In one of the embodiments, it further includes destroying the mother liquor in step (6).
附图说明Description of the drawings
为了更好地描述和说明这里公开的那些发明的实施例和/或示例,可以参考一幅或多幅附图。用于描述附图的附加细节或示例不应当被认为是对所公开的发明、目前描述的实施例和/或示例以及目前理解的这些发明的最佳模式中的热河一者的范围的限制。In order to better describe and illustrate the embodiments and/or examples of the inventions disclosed herein, one or more drawings may be referred to. The additional details or examples used to describe the drawings should not be considered as limiting the scope of the disclosed invention, the currently described embodiments and/or examples, and the best mode of these inventions currently understood. .
图1为本申请的连续式氨解反应系统示意图。Figure 1 is a schematic diagram of the continuous ammonolysis reaction system of the application.
图2为本申请的牛磺酸生产工艺示意图。Figure 2 is a schematic diagram of the taurine production process of the application.
图中:10、进料装置;20、高压反应装置;30、缓冲装置;40、闪蒸装置;50、氨回收装置;60、第一进料管;70、第二进料管;80、酸化装置;90、分离装置;100、母液回收装置;110、焚烧炉;120、结晶装置;130、调整装置;200、氨化高压釜。In the figure: 10, 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.
具体实施方式Detailed ways
以下将对本申请提供的连续式氨解反应系统、牛磺酸碱金属盐及牛磺酸的制备方法作进一步说明。The continuous ammonolysis reaction system, the alkali metal salt of taurine and the preparation method of taurine provided in the present application will be further described below.
请参照图1,为本申请提供的连续式氨解反应系统,所述连续式氨解反应系统用于进行氨解反应生成目标产品,提高目标产品的收率和待反应原料的转化率,以及提高工艺的产能、安全性、稳定性和可靠性。Please refer to Figure 1, the continuous ammonolysis reaction system provided for this application, 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.
在一个或多个实施例中,所述连续式氨解反应系统包括依次串联连接的高压反应装置20、缓冲装置30和闪蒸装置40。In one or more embodiments, 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.
其中,所述高压反应装置20包括n台氨化高压釜200,第1台所述氨化高压釜200至第n台所述氨化高压釜200依次串联,所述氨化高压釜200为氨解反应的容器,所述氨解反应采用氨作为氨化剂。从而,多台串联的氨化高压釜200同时用于氨解反应时,既能保证与釜式间歇反应相应的压力、温度及维持时间,又能达到管道式连续反应的产能。而且,由于多台氨化高压釜200串联构成了一台超大容积的高压反应器,利用连续反应的产能优势,可以延长待反应原料的停留时间,使待反应原料能够充分反应,并降低对反应条件的要求。Wherein, 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. Moreover, since multiple ammoniating autoclaves 200 are connected in series to form a large-volume high-pressure reactor, the advantage of continuous reaction production capacity can prolong the residence time of the raw materials to be reacted, so that the raw materials to be reacted can fully react and reduce the reaction time. Conditional requirements.
在高压反应装置20中,2台及以上的氨化高压釜200进行串联即可满足使用的需求,即n≥2。而考虑到连续反应的产能以及目标产品的收率和原料的转化率,优选3台-8台的氨化高压釜200串联使用,更优选6台氨化高压釜200串联使用。In the high-pressure reaction device 20, two or more ammoniating autoclaves 200 can be connected in series to meet the requirements of use, that is, n≥2. Considering the production capacity of the continuous reaction, the yield of the target product and the conversion rate of the raw materials, it is preferable to use three to eight ammoniating autoclaves 200 in series, and it is more preferable to use six ammoniating autoclaves 200 in series.
在一个或多个实施例中,所述氨化高压釜的体积为0.5m 3-5m 3In one or more embodiments, the volume of the ammoniated autoclave is 0.5 m 3 -5 m 3 .
在一个或多个实施例中,第1台所述氨化高压釜200连接有进料装置10,第1台所述氨化高压釜200至第n台所述氨化高压釜200均连接有第一进料管60,每一所述氨化高压釜200均连接有第二进料管70。In one or more embodiments, 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.
其中,所述进料装置10用于引入氨解反应的氨源,如氨水,所述第一进料管60用于补充氨解反应过程中消耗的氨,如液氨,所述第二进料管70用于提供氨解反应所需的待反应原料,如羟乙基磺酸碱金属盐等,从而,可以通过进料装置10、第一进料管60和第二进料管70的精确控制使每一氨解反应过程中氨与待反应原料的摩尔比达到极大值,进而提高目标产品的收率和待反应原料的转化率。Wherein, 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, and 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.
在一个或多个实施例中,所述缓冲装置30与第n台所述氨化高压釜200连接,用于接收第1台至第n台所述氨化高压釜200中氨解反应后的混合物料。第1台所述氨化高压釜200至第n台所述氨化高压釜200之间压力相差很小,从而,可以利用第n台所述氨化高压釜200与所述缓冲装置30之间的压力差,使得所述氨化高压釜200中反应液按串联的顺序流动,进入缓冲装置30中。因而,可以通过缓冲装置30控制氨化高压釜200中的进出料,提高连续式氨解反应系统的安全性,使得本申请连续式氨解反应系统可以连续运转,以实现连续化生产。In one or more embodiments, 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.
由于第n台所述氨化高压釜200与所述缓冲装置30之间的压力差会使得未反应的氨源或者未完全反应的反应液提前进入缓冲装置30中,所以,所述缓冲装置30还设有排料管,用于排除收集到的欠佳的混合物料。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.
在具体使用时,待氨化高压釜200中的氨解反应进行一定时间后或者氨解反应稳定后,开启缓冲装置30的排料管排除收集到的欠佳的混合物料,然后关闭排料管进行重新收集,得到混合物料。In specific use, after the ammonolysis reaction in the ammonification autoclave 200 has progressed for a certain period of time or after the ammonolysis reaction has stabilized, 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.
在一个或多个实施例中,所述闪蒸装置40与所述缓冲装置30连接,用于接收所述缓冲装置30中的所述混合物料并用于闪蒸得到氨解产物。In one or more embodiments, 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.
在具体使用时,当缓冲装置30与第n台氨化高压釜200的压力平衡后,缓冲装置30的进料阀关闭,出料阀开启,缓冲装置30中的混合物料利用压力差进入闪蒸装置40中,此时,停止氨化高压釜200的进料以暂停氨解反应的进行。当缓冲装置30与闪蒸装置40的压力平衡后,将缓冲装置30的出料阀关闭、进料阀开启,此时,重新开启氨化高压釜200的进料以使氨解反应重新进行,依此不断循环,实现连续化生产。In specific use, when the pressures of the buffer device 30 and the n-th ammoniating autoclave 200 are balanced, 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. In the device 40, at this time, the feeding of the ammonification autoclave 200 is stopped to suspend the progress of the ammonolysis reaction. After the pressures of the buffer device 30 and the flashing device 40 are balanced, the discharge valve of the buffer device 30 is closed and the feed valve is opened. At this time, the feed of the ammoniating autoclave 200 is reopened to restart the ammonolysis reaction. Continue to circulate accordingly to achieve continuous production.
在一个或多个实施例中,缓冲装置30的进料阀和出料阀可以利用自动切断阀进行自动控制。In one or more embodiments, the feed valve and the discharge valve of the buffer device 30 may be automatically controlled by an automatic shut-off valve.
混合物料在所述闪蒸装置40中闪蒸时,除了得到氨解产物还得到过量的氨。在一个或多个实施例中,所述连续式氨解反应系统还包括有氨回收装置50,所述氨回收装置50与所述闪蒸装置40连接,所述氨回收装置50用于回收所述闪蒸装置40中的氨,得到回收氨,所述回收氨可以为液氨,也可以为氨水。When the mixed material is flashed in the flashing device 40, in addition to the ammonolysis product, an excessive amount of ammonia is also obtained. In one or more embodiments, 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.
在一个或多个实施例中,所述氨回收装置50还与所述进料装置10连接,以将所述回收氨输送至所述进料装置10循环使用,以减少氨水的额外补充和液氨的使用,降低生产成本。In one or more embodiments, 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.
本申请连续式氨解反应系统在使用时,每台氨化高压釜200的反应时间由所串联的氨化高压釜200的台数、体积大小和原料的流速决定,每台氨化高压釜200中都在不断的进行氨解反应,可以使上一台氨化高压釜200中未反应完毕的待反应原料利用出料的时间完全反应,直到第n台氨化高压釜200中的待反应原料完全反应,出料至缓冲装置30中得到混合物料。When the continuous ammonolysis reaction system of the present application is in use, 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.
当第n台氨化高压釜200中具有未反应完毕的待反应原料时,这些未反应完毕的待反应原料无法利用出料的时间完成反应。所以,为了保证第n台氨化高压釜200中的待反应原料能够完全反应,可以降低第n台氨化高压釜200中的待反应原料的进入量。When there are unreacted raw materials to be reacted in the n-th ammoniating autoclave 200, these unreacted raw materials to be reacted cannot use the time of discharging to complete the reaction. Therefore, in order to ensure that the raw materials to be reacted in the n-th ammoniating autoclave 200 can be completely reacted, the input amount of the raw materials to be reacted in the n-th ammoniating autoclave 200 can be reduced.
或者,所述连续式氨解反应系统还包括有调整装置130,所述调整装置130串联于第n台所述氨化高压釜200,所述缓冲装置30串联于所述调整装置130,所述调整装置130为氨解反应的容器,使第n台氨化高压釜200中未反应完毕的待反应原料在调整装置130中完成反应。Alternatively, 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.
为了使第n台氨化高压釜200中未反应完毕的待反应原料能够在调整装置130中完成反应,所述调整装置130还连接有第一进料管60,用于向所述调整装置130补充氨解反应过程中消耗的氨。In order to enable the unreacted raw materials to be reacted in the n-th ammoniated autoclave 200 to complete the reaction 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.
请继续参照图1,本申请还提供一种牛磺酸碱金属盐的制备方法,所述制备方法采用上述的连续式氨解反应系统,所述制备方法包括以下步骤:Please continue to refer to FIG. 1, 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:
(1)通过所述进料装置10向第1台所述氨化高压釜200中提供氨水,以使串联的每一所述氨化高压釜200均充有氨水;(1) Supplying ammonia water to the first ammoniating autoclave 200 through the feeding device 10, so that each ammoniating autoclave 200 connected in series is filled with ammonia water;
(2)在反应温度和反应压力下,通过所述进料装置10向第1台所述氨化高压釜200提供 氨水,通过所述第一进料管60向第1台所述氨化高压釜200至第n台所述氨化高压釜200提供氨源,通过所述第二进料管70向每一所述氨化高压釜200提供羟乙基磺酸碱金属盐溶液,以使每一所述氨化高压釜200均进行氨解反应并使反应液以串联的顺序进入所述缓冲装置30中,得到混合物料;(2) Under the reaction temperature and reaction pressure, 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;
(3)所述缓冲装置30与第n台所述氨化高压釜200的压力平衡后,停止所述进料装置10向第1台所述氨化高压釜提供氨水,停止所述第一进料管60向第1台所述氨化高压釜200至第n台所述氨化高压釜200提供氨源,停止所述第二进料管70向每一所述氨化高压釜200提供羟乙基磺酸碱金属盐溶液,并使所述缓冲装置30中的混合物料进入所述闪蒸装置40中;(3) After the pressures of the buffer device 30 and the n-th ammoniating autoclave 200 are balanced, 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;
(4)所述闪蒸装置40与所述缓冲装置30的压力平衡后,使所述缓冲装置30中的混合物料停止进入所述闪蒸装置40中;(4) After the pressures of the flashing device 40 and the buffering device 30 are balanced, stop the mixed material in the buffering device 30 from entering the flashing device 40;
(5)将所述闪蒸装置40中的混合物料降压闪蒸,得到氨解产物,所述氨解产物包括牛磺酸碱金属盐。(5) 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.
步骤(1)中,所述氨水由液氨、氨水、水中的至少两种在进料装置10中配置得到,氨的质量浓度为25%-50%。In 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%.
n台所述氨化高压釜200串联连接时,通过所述进料装置10向第1台所述氨化高压釜200提供氨水即可使每一氨化高压釜200均充有氨水。在一个或多个实施例中,所述氨化高压釜200中氨水的体积为所述氨化高压釜200的体积的60%-90%。When n sets of the ammoniating autoclaves 200 are connected in series, the feeding device 10 provides ammonia water to the first ammoniating autoclave 200 so that each ammoniating autoclave 200 is filled with ammonia water. In one or more embodiments, the volume of ammonia in the ammoniating autoclave 200 is 60%-90% of the volume of the ammoniating autoclave 200.
步骤(2)中,所述反应温度为250℃-290℃,所述反应压力为14MPa-24MPa,每一所述氨化高压釜200的转速为100r/min-500r/min。In step (2), the reaction temperature is 250° C. to 290° C., the reaction pressure is 14 MPa to 24 MPa, and the rotation speed of each ammoniating autoclave 200 is 100 r/min to 500 r/min.
第一进料管60向第1台所述氨化高压釜200至第n台所述氨化高压釜200提供的氨源优选为液氨。因为,羟乙基磺酸碱金属盐在氨解时消耗的是氨,如果第一进料管60补加氨水,会使氨化高压釜200中反应体积越来越多。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.
第二进料管70向每一氨化高压釜200提供的羟乙基磺酸碱金属盐溶液包括羟乙基磺酸钠溶液、羟乙基磺酸钾溶液、羟乙基磺酸锂溶液中的至少一种,优选为羟乙基磺酸钠溶液,羟乙基磺酸碱金属盐溶液中羟乙基磺酸碱金属的质量浓度为30%-60%。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%.
所述进料装置10向第1台所述氨化高压釜200提供氨水的速度为6.0m 3/h-10.0m 3/h,所述第一进料管60向第1台所述氨化高压釜200至第n台所述氨化高压釜200提供氨源的速度均为0.1m 3/h-0.2m 3/h,所述第二进料管70向每一所述氨化高压釜200提供羟乙基磺酸碱金属盐溶液的速度均为0.1m 3/h-0.3m 3/h。 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.
在一个或多个实施例中,所述第二进料管70向每一所述氨化高压釜200提供羟乙基磺酸碱金属盐溶液的方式为滴加,所述第一进料管60向第1台所述氨化高压釜200至第n台所述氨化高压釜200提供氨源的方式也可以为滴加。In one or more embodiments, 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.
从而,所述制备方法可以通过对进料装置10、第一进料管60和第二进料管70的进料速度的精确控制,使每一氨化高压釜中的氨与羟乙基磺酸碱金属盐的摩尔比达到极大值,以大幅度降低二牛磺酸碱金属盐等副产物的产生,使牛磺酸碱金属盐的收率达到90%以上,羟乙基磺酸碱金属盐的转化率超过95%。而且,工艺安全稳定,产品组成成分稳定,再现性高。Therefore, 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%. Moreover, the process is safe and stable, the product composition is stable, and the reproducibility is high.
同时,通过控制所串联的氨化高压釜200的台数、体积大小,以及进料装置10、第一进料管60和第二进料管70的进料速度,可调整氨化高压釜200中反应液的停留时间。At the same time, by controlling the number and volume of the ammoniated autoclaves 200 connected in series, as well as the feeding speed of the feeding device 10, the first feeding pipe 60 and the second feeding pipe 70, the contents of the ammoniating autoclave 200 can be adjusted. The residence time of the reaction solution.
应予说明的是,第一进料管60和第二进料管70向每一氨化高压釜200中提供液氨和羟乙基磺酸碱金属盐溶液的速度是可以相同,也可以不同的。It should be noted that 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.
当反应液在氨化高压釜200中的停留时间足够使羟乙基磺酸碱金属盐完全反应时,可使第二进料管70向每一氨化高压釜200中提供羟乙基磺酸碱金属盐溶液的速度保持相同。When the residence time of the reaction liquid in the ammoniating autoclave 200 is sufficient to completely react the alkali metal salt of isethionate, 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.
当反应液在氨化高压釜200中的停留时间短时,为了保证第n台氨化高压釜200中的羟乙基磺酸碱金属盐能够完全反应,可以降低第n台氨化高压釜200中的羟乙基磺酸碱金属盐的进入量。甚至,可以从第1台氨化高压釜200开始,顺次降低每一台氨化高压釜200中羟乙基磺酸碱金属的进入量。When the residence time of the reaction liquid in the ammoniating autoclave 200 is short, in order to ensure that the alkali metal isethionate in the nth ammoniating autoclave 200 can completely react, the nth ammoniating autoclave 200 can be reduced. The amount of isethionate alkali metal salt in it. Even, starting from the first ammoniating autoclave 200, the amount of alkali metal isethionate in each ammoniating autoclave 200 can be sequentially reduced.
或者,当连续式氨解反应系统包括有调整装置130时,调整装置130在步骤(1)的进料过程中也会充有氨水,所以,步骤(2)中可使每一所述氨化高压釜200中的反应液以串联的顺序进入所述调整装置130,使反应液中未完全反应的羟乙基磺酸碱金属盐在所述调整装置130中反应完全,再通过所述调整装置130进入所述缓冲装置30,得到混合物料。Or, 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.
此时,步骤(2)中还通过所述第一进料管60以连续式或者间歇式的方式向所述调整装置130提供氨源,以补充氨解反应消耗的氨。At this time, in 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.
步骤(2)中,待氨化高压釜200中的氨解反应进行一定时间后或者氨解反应稳定后,还可以包括开启缓冲装置30的排料管排除收集到的欠佳的混合物料,然后关闭排料管进行重新收集,得到质量较佳的混合物料。In 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.
步骤(5)中,还通过所述氨回收装置50回收降压闪蒸后的氨,得到回收氨,所述回收 氨可以为氨水,也可以为液氨,考虑到成本,在一个或多个实施例中,采用水循环回收降压闪蒸后的氨得到氨水。In step (5), 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. Considering the cost, one or more In the embodiment, water circulation is used to recover the ammonia after the depressurization and flash evaporation to obtain ammonia water.
在一个或多个实施例中,所述回收氨提供至所述进料装置10循环使用,以减少进料装置10中液氨的使用,降低生产成本。In one or more embodiments, 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.
由于进料装置10在步骤(2)中补加的是氨水,第一进料管60在步骤(2)中补加的液氨,所以,可以维持每一氨化高压釜200在氨解反应过程中的反应液的体积。从而,参照连续式氨解反应系统的具体使用,在进行步骤(5)时,可以重新开始步骤(2),依次循环,以实现牛磺酸碱金属盐的连续化生产。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.
请参照图2,本申请还提供一种牛磺酸的制备方法,包括所述牛磺酸碱金属盐的制备方法,以及Please refer to Figure 2, this application also provides a method for preparing taurine, including the method for preparing the alkali metal salt of taurine, and
(6)将所述氨解产物进行酸化,分离,得到固体产物和母液;(6) Acidifying and separating the ammonolysis product to obtain a solid product and mother liquor;
(7)将所述固体产物结晶,得到牛磺酸。(7) Crystallize the solid product to obtain taurine.
步骤(6)中,具体可以采用硫酸、盐酸等在酸化装置80中对所述氨解产物进行酸化,得到固液分明的酸化产物,经分离装置90分离后,得到固体产物和母液。In 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.
由于采用本申请的连续式氨解反应系统制备得到的氨解产物中主要为牛磺酸碱金属盐,羟乙基磺酸碱金属盐、二牛磺酸碱金属盐和三牛磺酸碱金属盐含量极低,所以,分离固体产物后,可以直接销毁步骤(6)中所述母液,不用对母液进行循环套用,不仅简化了工艺,而且避免了母液套用所带来的稳定性问题和安全隐患,使得生产工艺更加安全、稳定、可靠。Since the 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.
进一步地,销毁母液的方式很多,在一个或多个实施例中,采用母液回收装置100回收分离装置90分离得到的母液,并输送至焚烧炉110进行焚烧。Further, there are many ways to destroy the mother liquor. In one or more embodiments, 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.
步骤(7)中,所述固体产物具体可以在结晶装置120中降温析晶得到牛磺酸粗品,所述牛磺酸粗品再经纯化后得到牛磺酸纯品。In 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.
以下,将通过以下具体实施例对所述连续式氨解反应系统、牛磺酸碱金属盐及牛磺酸的制备方法做进一步的说明。Hereinafter, the continuous ammonolysis reaction system, the alkali metal salt of taurine, and the preparation method of taurine will be further described through the following specific examples.
以下实施例的连续式氨解反应系统均使用6台5.0m 3的氨化高压釜串联在一起,串联的氨化高压釜均为上部进料、插底管底部出料的形式,用高压管道相互连接。用高压泵和进料装置将氨水压入第1台氨化高压釜内,用第一进料管向第1台至第6台氨化高压釜滴加液氨,用高压泵和第二进料管向第1台至第6台氨化高压釜滴加羟乙基磺酸钠水溶液。串联的 第1台至第6台氨化高压釜之间压力相差很小,利用第6台氨化高压釜出料产生的压差,使氨化高压釜中的反应液按串联的顺序向缓冲装置流动。 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.
实施例1Example 1
采用液氨和水配置浓度为40%的氨水,采用羟乙基磺酸钠固体和水配置浓度为40%的羟乙基磺酸钠水溶液。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.
将配置好的浓度为40%的氨水通过高压泵和进料装置将其压入第1台氨化高压釜内,使串联的第1台至第6台氨化高压釜内的氨水达到釜体积的80%时,停止加料。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.
开启搅拌装置,使第1台至第6台氨化高压釜转速达到250r/min时,开始对第1台至第6台氨化高压釜加热升温,利用出料阀控制系统中氨化高压釜的压力。当第1台至第6台氨化高压釜的温度升至250℃,压力至14.5MPa时,通过高压泵和进料装置向第1台氨化高压釜加入40%氨水,并通过高压泵和第二进料管向第1台至第6台氨化高压釜滴加40%的羟乙基磺酸钠水溶液进行氨解反应,同时通过第一进料管向第1台至第6台氨化高压釜滴加液氨,以补充反应过程消耗的氨,其中,进料装置中氨水的流速为10.0m 3/h,第一进料管中液氨的流速为0.10m 3/h,第二进料管中羟乙基磺酸钠水溶液的流速为0.22m 3/h。 Turn on the stirring device to make the speed of the first to sixth ammoniating autoclaves reach 250r/min, start to heat up the first to sixth ammoniating autoclaves, and use the discharge valve to control the ammoniating autoclave in the system pressure. When the temperature of the first to sixth ammoniating autoclaves rises to 250°C and the pressure reaches 14.5MPa, 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 40% sodium isethionate aqueous solution into the 1st to 6th ammoniated autoclaves to carry out the ammonolysis reaction, and at the same time passes the first feed pipe to the 1st to 6th ammonia Liquid ammonia is added dropwise to the autoclave to supplement the ammonia consumed in the reaction process. 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.
随着氨解反应的进行,第1台氨化高压釜至第6台氨化高压釜内的反应液按串联顺序流动,经过缓冲装置的进料阀进入缓冲装置,缓冲装置收集得到混合物料。当缓冲装置的压力至14.5MPa时,与第6台氨化高压釜的压力达到平衡,关闭缓冲装置的进料阀,开启缓冲装置的出料阀,将混合物料压进闪蒸装置。当缓冲装置与闪蒸装置的压力平衡后,关闭缓冲装置的出料阀,开启缓冲装置的进料阀,使进料装置、第一进料管和第二进料管向氨化高压釜中进行再次进料,依此不断循环。With the progress of the ammonolysis reaction, 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. When 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. When 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.
闪蒸装置内的混合物料经降压闪蒸,获得氨解产物,并使用水循环回收其中的过量氨至氨回收装置,形成的氨水重新循环至进料装置继续使用。系统连续运行8小时后,取样分析,并计算,结果如表1所示。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.
表1Table 1
物料materials 百分比percentage
牛磺酸钠含量Sodium taurate content 87.07%87.07%
二牛磺酸钠含量Sodium ditaurate content 7.79%7.79%
三牛磺酸钠含量Sodium Tritaurate Content 0.53%0.53%
羟乙基磺酸钠含量Sodium isethionate content 4.61%4.61%
牛磺酸钠收率Yield of Sodium Taurate 90.72%90.72%
羟乙基磺酸钠转化率Conversion rate of sodium isethionate 95.23%95.23%
闪蒸后的氨解产物转入酸化装置中,滴加浓H 2SO 4进行酸化,直至pH=5.6时,停止滴加浓H 2SO 4,得到固液分明的酸化产物。将酸化产物采用分离装置分离后,固体产物转入结晶装置中,降温析晶得到牛磺酸粗品,牛磺酸粗品再经纯化后得到牛磺酸纯品。母液则经母液回收装置回收后进入焚烧装置进行焚烧处理,不进行母液套用。 The flashed ammonolysis product is transferred to the acidification device, and concentrated H 2 SO 4 is added dropwise for acidification, until the pH=5.6, the dropwise addition of concentrated H 2 SO 4 is stopped to obtain a solid-liquid acidification product. After 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.
最后,对牛磺酸纯品进行分析得到,牛磺酸纯品中牛磺酸的含量为99.96%,羟乙基磺酸钠的含量为0.02%,二牛磺酸钠和三牛磺酸钠未检出,其它杂质的含量为0.02%。Finally, 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%.
实施例2Example 2
采用液氨和水配置浓度为40%的氨水,采用羟乙基磺酸钠固体和水配置浓度为50%的羟乙基磺酸钠水溶液。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.
将配置好的浓度为40%的氨水通过高压泵和进料装置将其压入第1台氨化高压釜内,使串联的第1台至第6台氨化高压釜内的氨水达到釜体积的80%时,停止加料。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.
开启搅拌装置,使第1台至第6台氨化高压釜转速达到300r/min时,开始对第1台至第6台氨化高压釜加热升温,利用出料阀控制系统中氨化高压釜的压力。当第1台至第6台氨化高压釜的温度升至265℃,压力至18.3MPa时,通过高压泵和进料装置向第1台氨化高压釜加入40%氨水,并通过高压泵和第二进料管向第1台至第6台氨化高压釜滴加50%的羟乙基磺酸钠水溶液进行氨解反应,同时通过第一进料管向第1台至第6台氨化高压釜滴加液氨,以补充反应过程消耗的氨,其中,进料装置中氨水的流速为8.0m 3/h,第一进料管中液氨的流速为0.1m 3/h,第二进料管中羟乙基磺酸钠水溶液的流速为0.11m 3/h。 Turn on 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. When the temperature of the first to sixth ammoniating autoclaves rise to 265°C and the pressure to 18.3MPa, 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.
随着氨解反应的进行,第1台氨化高压釜至第6台氨化高压釜内的反应液按串联顺序流动,经过缓冲装置的进料阀进入缓冲装置,缓冲装置收集得到混合物料。当缓冲装置的压力至18.3MPa时,与第6台氨化高压釜的压力达到平衡,关闭缓冲装置的进料阀,开启缓冲装置的出料阀,将混合物料压进闪蒸装置。当缓冲装置与闪蒸装置的压力平衡后,关闭缓冲装置的出料阀,开启缓冲装置的进料阀,使进料装置、第一进料管和第二进料管向氨化高压釜中进行再次进料,依此不断循环。With the progress of the ammonolysis reaction, 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. When 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. When 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.
闪蒸装置内的混合物料经降压闪蒸,获得氨解产物,并使用水循环回收其中的过量氨 至氨回收装置,形成的氨水重新循环至进料装置继续使用。系统连续运行8小时后,取样分析,并计算,结果如表2所示。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.
表2Table 2
物料materials 百分比percentage
牛磺酸钠含量Sodium taurate content 93.57%93.57%
二牛磺酸钠含量Sodium ditaurate content 4.24%4.24%
三牛磺酸钠含量Sodium Tritaurate Content 0.43%0.43%
羟乙基磺酸钠含量Sodium isethionate content 1.76%1.76%
牛磺酸钠收率Yield of Sodium Taurate 95.75%95.75%
羟乙基磺酸钠转化率Conversion rate of sodium isethionate 98.21%98.21%
闪蒸后的氨解产物转入酸化装置中,滴加浓H 2SO 4进行酸化,直至pH=7.1时,停止滴加浓H 2SO 4,得到固液分明的酸化产物。将酸化产物采用分离装置分离后,固体产物转入结晶装置中,降温析晶得到牛磺酸粗品,牛磺酸粗品再经纯化后得到牛磺酸纯品。母液则经母液回收装置回收后进入焚烧装置进行焚烧处理,不进行母液套用。 The flashed ammonolysis product is transferred to the acidification device, and concentrated H 2 SO 4 is added dropwise for acidification, until the pH=7.1, the dropwise addition of concentrated H 2 SO 4 is stopped to obtain a solid-liquid acidification product. After 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.
最后,对牛磺酸纯品进行分析得到,牛磺酸纯品中牛磺酸的含量为99.91%,羟乙基磺酸钠的含量为0.02%,二牛磺酸钠和三牛磺酸钠未检出,其它杂质的含量为0.07%。Finally, 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%.
实施例3Example 3
采用液氨和水配置浓度为50%的氨水,采用羟乙基磺酸钠固体和水配置浓度为50%的羟乙基磺酸钠水溶液。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.
将配置好的浓度为50%的氨水通过高压泵和进料装置将其压入第1台氨化高压釜内,使串联的第1台至第6台氨化高压釜内的氨水达到釜体积的80%时,停止加料。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.
开启搅拌装置,使第1台至第6台氨化高压釜转速达到300r/min时,开始对第1台至第6台氨化高压釜加热升温,利用出料阀控制系统中氨化高压釜的压力。当第1台至第6台氨化高压釜的温度升至280℃,压力至18.6MPa时,通过高压泵和进料装置向第1台氨化高压釜加入50%氨水,并通过高压泵和第二进料管向第1台至第5台氨化高压釜滴加50%的羟乙基磺酸钠水溶液进行氨解反应,同时通过第一进料管向第1台至第6台氨化高压釜滴加液氨,以补充反应过程消耗的氨,其中,进料装置中氨水的流速为9.0m 3/h,第一进料管中液氨的流速为0.1m 3/h,第二进料管中羟乙基磺酸钠水溶液的流速为0.11m 3/h。 Turn on 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. When the temperature of the first to sixth ammoniating autoclaves rises to 280°C and the pressure reaches 18.6MPa, 50% ammonia water is added to the first ammoniating autoclave through the high-pressure pump and feeding device, and the high-pressure pump and The second feed pipe adds 50% sodium isethionate aqueous solution dropwise to the first to fifth ammoniated autoclaves to carry out the ammonolysis reaction, and at the same time to the first to sixth ammonia via the first feed pipe Liquid ammonia was added dropwise to the autoclave to supplement the ammonia consumed in the reaction process. Among them, the flow rate of ammonia in the feeding device was 9.0m 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.
随着氨解反应的进行,第1台氨化高压釜至第6台氨化高压釜内的反应液按串联顺序流动,经过缓冲装置的进料阀进入缓冲装置,缓冲装置收集得到混合物料。当缓冲装置的压力至18.6MPa时,与第6台氨化高压釜的压力达到平衡,关闭缓冲装置的进料阀,开启缓冲装置的出料阀,将混合物料压进闪蒸装置。当缓冲装置与闪蒸装置的压力平衡后,关闭缓冲装置的出料阀,开启缓冲装置的进料阀,使进料装置、第一进料管和第二进料管向氨化高压釜中进行再次进料,依此不断循环。With the progress of the ammonolysis reaction, 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. When 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. When 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.
闪蒸装置内的混合物料经降压闪蒸,获得氨解产物,并使用水循环回收其中的过量氨至氨回收装置,形成的氨水重新循环至进料装置继续使用。系统连续运行8小时后,取样分析,并计算,结果如表3所示。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 3.
表3table 3
物料materials 百分比percentage
牛磺酸钠含量Sodium taurate content 95.53%95.53%
二牛磺酸钠含量Sodium ditaurate content 3.00%3.00%
三牛磺酸钠含量Sodium Tritaurate Content 0.27%0.27%
羟乙基磺酸钠含量Sodium isethionate content 1.19%1.19%
牛磺酸钠收率Yield of Sodium Taurate 97.08%97.08%
羟乙基磺酸钠转化率Conversion rate of sodium isethionate 98.80%98.80%
闪蒸后的氨解产物转入酸化装置中,滴加浓H 2SO 4进行酸化,直至pH=7.0时,停止滴加浓H 2SO 4,得到固液分明的酸化产物。将酸化产物采用分离装置分离后,固体产物转入结晶装置中,降温析晶得到牛磺酸粗品,牛磺酸粗品再经纯化后得到牛磺酸纯品。母液则经母液回收装置回收后进入焚烧装置进行焚烧处理,不进行母液套用。 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. After 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.
最后,对牛磺酸纯品进行分析得到,牛磺酸纯品中牛磺酸的含量为99.92%,羟乙基磺酸钠的含量为0.02%,二牛磺酸钠和三牛磺酸钠未检出,其它杂质的含量为0.06%。Finally, 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%.
实施例4Example 4
采用液氨和水配置浓度为50%的氨水,采用羟乙基磺酸钠固体和水配置浓度为45%的羟乙基磺酸钠水溶液。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.
将配置好的浓度为50%的氨水通过高压泵和进料装置将其压入第1台氨化高压釜内,使串联的第1台至第6台氨化高压釜内的氨水达到釜体积的80%时,停止加料。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.
开启搅拌装置,使第1台至第6台氨化高压釜转速达到300r/min时,开始对第1台至第6台氨化高压釜加热升温,利用出料阀控制系统中氨化高压釜的压力。当第1台至第6台氨化高压釜的温度升至280℃,压力至19.2MPa时,通过高压泵和进料装置向第1台氨化高压釜加入50%氨水,并通过高压泵和第二进料管向第1台至第5台氨化高压釜滴加45%的羟乙基磺酸钠水溶液进行氨解反应,同时通过第一进料管向第1台至第6台氨化高压釜滴加液氨,以补充反应过程消耗的氨,其中,进料装置中氨水的流速为8.0m 3/h,第一进料管中液氨的流速为0.1m 3/h,第二进料管中羟乙基磺酸钠水溶液的流速为0.18m 3/h。 Turn on 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. When the temperature of the first to sixth ammoniating autoclaves rises to 280°C and the pressure reaches 19.2MPa, 50% ammonia water is added to the first ammoniating autoclave through the high-pressure pump and feeding device, and the high-pressure pump and The second feed pipe drips 45% sodium isethionate aqueous solution into the first to fifth 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 is added dropwise to the autoclave to supplement the ammonia consumed in the reaction process. Among them, the flow rate of ammonia in the feeding device is 8.0m 3 /h, and 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.
随着氨解反应的进行,第1台氨化高压釜至第6台氨化高压釜内的反应液按串联顺序流动,经过缓冲装置的进料阀进入缓冲装置,缓冲装置收集得到混合物料。当缓冲装置的压力至19.2MPa时,与第6台氨化高压釜的压力达到平衡,关闭缓冲装置的进料阀,开启缓冲装置的出料阀,将混合物料压进闪蒸装置。当缓冲装置与闪蒸装置的压力平衡后,关闭缓冲装置的出料阀,开启缓冲装置的进料阀,使进料装置、第一进料管和第二进料管向氨化高压釜中进行再次进料,依此不断循环。With the progress of the ammonolysis reaction, 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. When 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. When 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.
闪蒸装置内的混合物料经降压闪蒸,获得氨解产物,并使用水循环回收其中的过量氨至氨回收装置,形成的氨水重新循环至进料装置继续使用。系统连续运行8小时后,取样分析,并计算,结果如表4所示。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.
表4Table 4
物料materials 百分比percentage
牛磺酸钠含量Sodium taurate content 93.13%93.13%
二牛磺酸钠含量Sodium ditaurate content 3.78%3.78%
三牛磺酸钠含量Sodium Tritaurate Content 0.38%0.38%
羟乙基磺酸钠含量Sodium isethionate content 2.70%2.70%
牛磺酸钠收率Yield of Sodium Taurate 95.07%95.07%
羟乙基磺酸钠转化率Conversion rate of sodium isethionate 97.26%97.26%
闪蒸后的氨解产物转入酸化装置中,滴加浓H 2SO 4进行酸化,直至pH=7.0时,停止滴加浓H 2SO 4,得到固液分明的酸化产物。将酸化产物采用分离装置分离后,固体产物转入结晶装置中,降温析晶得到牛磺酸粗品,牛磺酸粗品再经纯化后得到牛磺酸纯品。母液则经母液回收装置回收后进入焚烧装置进行焚烧处理,不进行母液套用。 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. After 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.
最后,对牛磺酸纯品进行分析得到,牛磺酸纯品中牛磺酸的含量为99.90%,羟乙基 磺酸钠的含量为0.02%,二牛磺酸钠和三牛磺酸钠未检出,其它杂质的含量为0.08%。Finally, 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%.
实施例5Example 5
采用液氨和水配置浓度为50%的氨水,采用羟乙基磺酸钠固体和水配置浓度为45%的羟乙基磺酸钠水溶液。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.
将配置好的浓度为50%的氨水通过高压泵和进料装置将其压入第1台氨化高压釜内,使串联的第1台至第6台氨化高压釜内的氨水达到釜体积的80%时,停止加料。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.
开启搅拌装置,使第1台至第6台氨化高压釜转速达到300r/min时,开始对第1台至第6台氨化高压釜加热升温,利用出料阀控制系统中氨化高压釜的压力。当第1台至第6台氨化高压釜的温度升至280℃,压力至18.4MPa时,通过高压泵和进料装置向第1台氨化高压釜加入50%氨水,并通过高压泵和第二进料管向第1台至第5台氨化高压釜滴加45%的羟乙基磺酸钠水溶液进行氨解反应,同时通过第一进料管向第1台至第6台氨化高压釜滴加液氨,以补充反应过程消耗的氨,其中,进料装置中氨水的流速为8.0m 3/h,第一进料管中液氨的流速为0.1m 3/h,第二进料管中羟乙基磺酸钠水溶液的流速分别为0.22m 3/h、0.20m 3/h、0.18m 3/h、0.16m 3/h、0.14m 3/h。 Turn on 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. When the temperature of the first to sixth ammoniating autoclaves rise to 280°C and the pressure to 18.4 MPa, 50% ammonia water is added to the first ammoniating autoclave through the high-pressure pump and feeding device, and the high-pressure pump and The second feed pipe drips 45% sodium isethionate aqueous solution into the first to fifth ammoniated autoclaves for 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. 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.
随着氨解反应的进行,第1台氨化高压釜至第6台氨化高压釜内的反应液按串联顺序流动,经过缓冲装置的进料阀进入缓冲装置,缓冲装置收集得到混合物料。当缓冲装置的压力至18.4MPa时,与第6台氨化高压釜的压力达到平衡,关闭缓冲装置的进料阀,开启缓冲装置的出料阀,将混合物料压进闪蒸装置。当缓冲装置与闪蒸装置的压力平衡后,关闭缓冲装置的出料阀,开启缓冲装置的进料阀,使进料装置、第一进料管和第二进料管向氨化高压釜中进行再次进料,依此不断循环。With the progress of the ammonolysis reaction, 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. When 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. When 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.
闪蒸装置内的混合物料经降压闪蒸,获得氨解产物,并使用水循环回收其中的过量氨至氨回收装置,形成的氨水重新循环至进料装置继续使用。系统连续运行8小时后,取样分析,并计算,结果如表5所示。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 5.
表5table 5
物料materials 百分比percentage
牛磺酸钠含量Sodium taurate content 93.58%93.58%
二牛磺酸钠含量Sodium ditaurate content 3.62%3.62%
三牛磺酸钠含量Sodium Tritaurate Content 0.38%0.38%
羟乙基磺酸钠含量Sodium isethionate content 2.42%2.42%
牛磺酸钠收率Yield of Sodium Taurate 95.45%95.45%
羟乙基磺酸钠转化率Conversion rate of sodium isethionate 97.55%97.55%
闪蒸后的氨解产物转入酸化装置中,滴加浓H 2SO 4进行酸化,直至pH=7.0时,停止滴加浓H 2SO 4,得到固液分明的酸化产物。将酸化产物采用分离装置分离后,固体产物转入结晶装置中,降温析晶得到牛磺酸粗品,牛磺酸粗品再经纯化后得到牛磺酸纯品。母液则经母液回收装置回收后进入焚烧装置进行焚烧处理,不进行母液套用。 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. After 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.
最后,对牛磺酸纯品进行分析得到,牛磺酸纯品中牛磺酸的含量为99.90%,羟乙基磺酸钠的含量为0.02%,二牛磺酸钠和三牛磺酸钠未检出,其它杂质的含量为0.08%。Finally, 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%.
对比例Comparison
使用高压釜进行间歇氨化反应Use autoclave for batch ammoniation reaction
按常规的间歇釜式氨解反应工艺,将计量的羟乙基磺酸钠固体溶解于装有一定浓度氨水(25%-50%)高压釜中,于250℃-290℃、14MPa-25MPa反应条件下,进行氨化反应1小时-3小时,得到牛磺酸钠水溶液,经计算,牛磺酸钠的收率平均在77%-80%。According to the conventional batch-tank ammonolysis reaction process, the metered sodium isethionate solid is dissolved in an autoclave containing a certain concentration of ammonia water (25%-50%), and reacted at 250℃-290℃, 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.
由上述实施例和对比例可知,本申请制备方法的牛磺酸钠的收率在95%左右,远大于间歇釜式77%-80%的收率。由此可知,在牛磺酸的制备过程中,第一、羟乙基磺酸钠、二牛磺酸钠和三牛磺酸钠含量较少,有利于后期酸化、结晶、提纯,得到的牛磺酸含量接近100%,第二、可以避免复杂的母液套用过程,简化生产工艺,提高生产工艺的安全性、稳定性和可靠性。It can be seen from the foregoing examples and comparative examples that 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.
以上所述实施例的各技术特征可以进行任意的组合,为使描述简洁,未对上述实施例中的各个技术特征所有可能的组合都进行描述,然而,只要这些技术特征的组合不存在矛盾,都应当认为是本说明书记载的范围。The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, all possible combinations of the various technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, All should be considered as the scope of this specification.
以上所述实施例仅表达了本申请的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对申请专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本申请构思的前提下,还可以做出若干变形和改进,这些都属于本申请的保护范围。因此,本申请专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several implementation manners of the present application, and their description is relatively specific and detailed, but they should not be interpreted as a limitation on the scope of the patent application. It should be noted that for those of ordinary skill in the art, without departing from the concept of this application, several modifications and improvements can be made, and these all fall within the protection scope of this application. Therefore, the scope of protection of the patent of this application shall be subject to the appended claims.

Claims (18)

  1. 一种连续式氨解反应系统,其特征在于,包括:A continuous ammonolysis reaction system, characterized in that it comprises:
    高压反应装置,所述高压反应装置包括n台氨化高压釜,n≥2,第1台所述氨化高压釜至第n台所述氨化高压釜依次串联,所述氨化高压釜为氨解反应的容器,所述氨解反应采用氨作为氨化剂,第1台所述氨化高压釜连接有进料装置,第1台所述氨化高压釜至第n台所述氨化高压釜均连接有第一进料管,每一所述氨化高压釜均连接有第二进料管;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;
    缓冲装置,所述缓冲装置与第n台所述氨化高压釜连接,用于接收第1台至第n台所述氨化高压釜中氨解反应后的混合物料;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;
    闪蒸装置,所述闪蒸装置与所述缓冲装置连接,用于接收所述缓冲装置中的所述混合物料并通过闪蒸得到氨解产物。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.
  2. 根据权利要求1所述的连续式氨解反应系统,其特征在于,所述进料装置用于引入氨解反应的氨源,所述第一进料管用于补充氨解反应过程中消耗的氨,所述第二进料管用于提供氨解反应所需的待反应原料。The continuous ammonolysis reaction system according to claim 1, wherein the feeding device is used to introduce an ammonia source for the ammonolysis reaction, and the first feeding pipe is used to supplement the ammonia consumed in the ammonolysis reaction process. , The second feed pipe is used to provide raw materials to be reacted required for the ammonolysis reaction.
  3. 根据权利要求1所述的连续式氨解反应系统,其特征在于,所述连续式氨解反应系统还包括有氨回收装置,所述氨回收装置与所述闪蒸装置连接,所述氨回收装置用于回收所述闪蒸装置中的氨,得到回收氨。The continuous ammonolysis reaction system according to claim 1, wherein the continuous ammonolysis reaction system further comprises an ammonia recovery device, the ammonia recovery device is connected to the flashing device, and the ammonia recovery The device is used to recover the ammonia in the flash evaporation device to obtain recovered ammonia.
  4. 根据权利要求3所述的连续式氨解反应系统,其特征在于,所述氨回收装置还与所述进料装置连接,以将所述回收氨输送至所述进料装置。The continuous ammonolysis reaction system according to claim 3, wherein the ammonia recovery device is also connected to the feeding device to deliver the recovered ammonia to the feeding device.
  5. 根据权利要求1所述的连续式氨解反应系统,其特征在于,所述连续式氨解反应系统还包括有调整装置,所述调整装置串联于第n台所述氨化高压釜,所述缓冲装置串联于所述调整装置,所述调整装置为氨解反应的容器。The continuous ammonolysis reaction system according to claim 1, wherein the continuous ammonolysis reaction system further comprises an adjusting device, and the adjusting device is connected in series with the nth ammoniating autoclave, and The buffer device is connected in series with the adjustment device, and the adjustment device is a vessel for the ammonolysis reaction.
  6. 根据权利要求5所述的连续式氨解反应系统,其特征在于,所述调整装置连接有第一进料管。The continuous ammonolysis reaction system according to claim 5, wherein the adjusting device is connected with a first feed pipe.
  7. 一种牛磺酸碱金属盐的制备方法,其特征在于,所述制备方法采用权利要求1-6任意一项所述的连续式氨解反应系统,所述制备方法包括以下步骤:A preparation method of taurine alkali metal salt, characterized in that the preparation method adopts the continuous ammonolysis reaction system according to any one of claims 1 to 6, and the preparation method comprises the following steps:
    (1)通过所述进料装置向第1台所述氨化高压釜中提供氨水,以使串联的每一所述氨化高压釜均充有氨水;(1) Provide ammonia water to the first ammoniating autoclave through the feeding device, so that each ammoniating autoclave connected in series is filled with ammonia water;
    (2)在反应温度和反应压力下,通过所述进料装置向第1台所述氨化高压釜提供氨水,通过所述第一进料管向第1台所述氨化高压釜至第n台所述氨化高压釜提供氨源,通过所述第二进料管向每一所述氨化高压釜提供羟乙基磺酸碱金属盐溶液,以使每一所述氨化高压釜均进行氨解反应并使反应液以串联的顺序进入所述缓冲装置中,得到混合物料;(2) Under the reaction temperature and reaction pressure, 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;
    (3)所述缓冲装置与第n台所述氨化高压釜的压力平衡后,停止所述进料装置向第1台所述氨化高压釜提供氨水,停止所述第一进料管向第1台所述氨化高压釜至第n台所述氨化高压釜提供氨源,停止所述第二进料管向每一所述氨化高压釜提供羟乙基磺酸碱金属盐溶液,并使所述缓冲装置中的混合物料进入所述闪蒸装置中;(3) After the pressure of the buffer device and the n-th ammoniating autoclave is balanced, stop the feeding device to provide ammonia to the first ammoniating autoclave, and stop the first feeding pipe to supply ammonia to the first ammoniating autoclave. The first ammoniating autoclave to the nth ammoniating autoclave provide ammonia source, and the second feed pipe is stopped to provide alkali metal isethionate solution to each of the ammoniating autoclaves , And make the mixture material in the buffer device enter the flash evaporation device;
    (4)所述闪蒸装置与所述缓冲装置的压力平衡后,使所述缓冲装置中的混合物料停止进入所述闪蒸装置中;(4) After the pressures of the flashing device and the buffering device are balanced, stop the mixed material in the buffering device from entering the flashing device;
    (5)将所述闪蒸装置中的混合物料降压闪蒸,得到氨解产物,所述氨解产物包括牛磺酸碱金属盐。(5) Depressurizing and flashing the mixture in the flashing device to obtain an ammonolysis product, and the ammonolysis product includes an alkali metal salt of taurine.
  8. 根据权利要求7所述的牛磺酸碱金属盐的制备方法,其特征在于,步骤(1)中,所述氨化高压釜中氨水的体积为所述氨化高压釜的体积的60%-90%。The method for preparing an alkali metal salt of taurine according to claim 7, wherein in step (1), the volume of ammonia in the ammoniated autoclave is 60% to the volume of the ammoniated autoclave. 90%.
  9. 根据权利要求7所述的牛磺酸碱金属盐的制备方法,其特征在于,步骤(2)中,所述氨源包括液氨。The method for preparing an alkali metal salt of taurine according to claim 7, wherein in step (2), the ammonia source comprises liquid ammonia.
  10. 根据权利要求7所述的牛磺酸碱金属盐的制备方法,其特征在于,步骤(2)中,所述进料装置向第1台所述氨化高压釜提供氨水的速度为6.0m 3/h-10.0m 3/h,所述第一进料管向第1台所述氨化高压釜至第n台所述氨化高压釜提供氨源的速度均为0.1m 3/h-0.2m 3/h,所述第二进料管向每一所述氨化高压釜提供羟乙基磺酸碱金属盐溶液的速度均为0.1m 3/h-0.3m 3/h。 The method for preparing an alkali metal salt of taurine according to claim 7, wherein in step (2), the feeding device provides ammonia to the first ammoniating autoclave at a rate of 6.0 m 3 /h-10.0m 3 /h, the rate at which the first feed pipe provides ammonia source from the first ammoniating autoclave to the nth ammoniating autoclave is 0.1m 3 /h-0.2 m 3 / h, the second feed pipe provided isethionate alkali metal salt solution to each of the amides are autoclave speed 0.1m 3 /h-0.3m 3 / h.
  11. 根据权利要求7所述的牛磺酸碱金属盐的制备方法,其特征在于,步骤(2)中,所述第二进料管向每一所述氨化高压釜提供羟乙基磺酸碱金属盐溶液的方式为滴加。The method for preparing an alkali metal salt of taurine according to claim 7, characterized in that, in step (2), the second feed pipe provides alkali isethionate to each of the ammoniated autoclaves The method of the metal salt solution is dropwise addition.
  12. 根据权利要求7所述的牛磺酸碱金属盐的制备方法,其特征在于,步骤(2)中,每一所述氨化高压釜均进行氨解反应并使反应液以串联的顺序进入所述调整装置,再通过所述调整装置进入所述缓冲装置,得到混合物料。The method for preparing an alkali metal salt of taurine according to claim 7, characterized in that, in step (2), each of the ammoniated autoclaves is subjected to an ammonolysis reaction and the reaction liquid enters the plant in series. The adjusting device then enters the buffering device through the adjusting device to obtain the mixed material.
  13. 根据权利要求12所述的牛磺酸碱金属盐的制备方法,其特征在于,步骤(2)中,还包括通过所述第一进料管以连续式或者间歇式的方式向所述调整装置提供氨源。The method for preparing an alkali metal salt of taurine according to claim 12, characterized in that, in step (2), it further comprises feeding the adjusting device in a continuous or intermittent manner through the first feed pipe Provide ammonia source.
  14. 根据权利要求7所述的牛磺酸碱金属盐的制备方法,其特征在于,步骤(5)中,还通过所述氨回收装置回收降压闪蒸后的氨,得到回收氨。The method for preparing an alkali metal salt of taurine according to claim 7, characterized in that, in step (5), the ammonia after depressurization and flashing is also recovered by the ammonia recovery device to obtain recovered ammonia.
  15. 根据权利要求14所述的牛磺酸碱金属盐的制备方法,其特征在于,所述回收氨提供至所述进料装置。The method for preparing an alkali metal salt of taurine according to claim 14, wherein the recovered ammonia is supplied to the feeding device.
  16. 根据权利要求7所述的牛磺酸碱金属盐的制备方法,其特征在于,在进行步骤(5)时,重新开始步骤(2)。The method for preparing an alkali metal salt of taurine according to claim 7, wherein when step (5) is performed, step (2) is restarted.
  17. 一种牛磺酸的制备方法,其特征在于,所述制备方法包括权利要求7-16任意一项所述牛磺酸碱金属盐的制备方法,以及A preparation method of taurine, characterized in that the preparation method comprises the preparation method of the alkali metal salt of taurine according to any one of claims 7-16, and
    (6)将所述氨解产物进行酸化,分离,得到固体产物和母液;(6) Acidifying and separating the ammonolysis product to obtain a solid product and mother liquor;
    (7)将所述固体产物结晶,得到牛磺酸。(7) Crystallize the solid product to obtain taurine.
  18. 根据权利要求17所述牛磺酸的制备方法,其特征在于,还包括销毁步骤(6)中所述母液。The method for preparing taurine according to claim 17, characterized in that it further comprises destroying the mother liquor in step (6).
PCT/CN2020/112059 2019-12-27 2020-08-28 Continuous ammonolysis reaction system, preparation method for taurine alkali metal salt and taurine WO2021128917A1 (en)

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