CN111087319A - Method for continuously preparing glycine in alcohol phase - Google Patents
Method for continuously preparing glycine in alcohol phase Download PDFInfo
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- CN111087319A CN111087319A CN201911384262.1A CN201911384262A CN111087319A CN 111087319 A CN111087319 A CN 111087319A CN 201911384262 A CN201911384262 A CN 201911384262A CN 111087319 A CN111087319 A CN 111087319A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
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Abstract
The invention provides a method for continuously preparing glycine in an alcohol phase, which comprises the following systems: a batching system, a continuous reactor and a solid-liquid separator; the batching system, the continuous reactor and the solid-liquid separator are communicated in sequence, and mother liquor separated by the solid-liquid separator returns to the batching system; the batching system comprises a urotropine batching tank and a chloroacetic acid batching tank, wherein the urotropine batching tank and the chloroacetic acid batching tank are respectively connected with a continuous reactor through pipelines, and the continuous reactor is a tube-type reactor or a tower-type reactor; the height-diameter ratio of each pipe in the tubular reactor is 20-30: 1, the height-diameter ratio of the tower reactor is 15-25: 1. the glycine preparation method provided by the invention can realize continuous production of glycine, solves the problems of back mixing and long retention time in the existing kettle type reaction process, and can improve the production efficiency and reduce the cost.
Description
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to a method for continuously preparing glycine in an alcohol phase.
Background
Glycine is an important raw material for producing products such as glyphosate, glycine ethyl ester hydrochloride and the like, and can also be used in the fields of food, feed and the like. The domestic main production method comprises the following steps: chloroacetic acid is used as a raw material and is subjected to ammonolysis reaction with liquid ammonia under the catalytic action of hexamethylenetetramine (urotropine), so that ammonium chloride is coproduced while glycine is produced. The method is generally adopted in China for water phase reaction, and glycine is obtained by separating a large amount of methanol after the reaction is finished; the method not only needs to consume a large amount of energy to recover the methanol, but also causes the decomposition of the urotropine and generates a large amount of waste water containing organic matters in the process of recovering the ammonium chloride, thereby polluting the environment and increasing the production cost.
In recent years, a process for producing glycine using methanol as a solvent has been reported. In the ammonolysis reaction, glycine and ammonium chloride are simultaneously separated out in a mixed crystal mode, and the obtained mixed crystal is separated after the reaction is finished. In the prior art, a batch kettle type reaction is utilized, ammonia gas is introduced into a methanol solution of chloroacetic acid and urotropine to obtain mixed crystals and a mother solution, and centrifugal separation is carried out. However, the batch still requires a long time for cooling after the reaction is completed, and there are risks of back mixing, long residence time and runaway of heat release, which results in long reaction period and high production cost. Because the feeding materials before the reaction are all liquid, and the solid-liquid mixture is obtained after the reaction, the reaction carried out by using the common tubular reactor and the common tower reactor is easy to cause the accumulation and back mixing of the discharging port, and the continuous production can not be smoothly realized.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a method for continuously preparing glycine in an alcohol phase, so as to improve the production efficiency of the glycine.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a method for continuously preparing glycine in an alcohol phase comprises the following systems: a batching system, a continuous reactor and a solid-liquid separator; the batching system, the continuous reactor and the solid-liquid separator are communicated in sequence, and mother liquor separated by the solid-liquid separator returns to the batching system; the batching system comprises a urotropine batching tank and a chloroacetic acid batching tank, wherein the urotropine batching tank and the chloroacetic acid batching tank are respectively communicated with the continuous reactor through pipelines, and the continuous reactor is a tube-type reactor or a tower-type reactor. Preferably, urotropine batching tank and chloroacetic acid batching tank comprise reation kettle and head tank, pass through the pipe connection between reation kettle and the head tank, and the solid is carried in the head tank through the pipeline by the pump after dissolving in reation kettle.
Further, the height-diameter ratio of each pipe in the tubular reactor is 20-30: 1.
further, the height-diameter ratio of the tower reactor is 15-25: 1.
further, the preparation method comprises the following steps:
(1) dissolving urotropine solid and chloroacetic acid solid in a urotropine mixing tank and a chloroacetic acid mixing tank respectively by using methanol; preferably, the solid urotropine is dissolved in a reaction kettle of a urotropine mixing tank by using methanol, and the dissolved solid is pumped into a raw material tank of the urotropine mixing tank by a pump after the dissolution is finished, wherein the raw material tank is communicated with a continuous reactor through a pipeline, and a flowmeter and a valve are arranged between the raw material tank and the continuous reactor, so that the amount of the urotropine entering the continuous reactor can be controlled; preferably, the chloroacetic acid solid is dissolved in a reaction kettle of a chloroacetic acid batching tank by using methanol, and the chloroacetic acid solid is pumped into a raw material tank of the chloroacetic acid batching tank by a pump after the dissolution is finished, wherein the raw material tank is communicated with the continuous reactor through a pipeline, and a flowmeter and a valve are arranged between the raw material tank and the continuous reactor, so that the amount of the chloroacetic acid entering the continuous reactor can be controlled;
(2) materials in the urotropine batching tank and the chloroacetic acid batching tank are pumped into the continuous reactor from the top of the continuous reactor, and liquid ammonia is pumped into the continuous reactor from the bottom of the continuous reactor;
(3) the lower half part of the continuous reactor is provided with a discharge hole, and the reacted materials in the continuous reactor are pumped into a solid-liquid separator to realize solid-liquid separation in the solid-liquid separator; preferably, the solid-liquid separator comprises a mother liquor tank and a centrifuge or a decanter, the reaction product of the continuous reactor is subjected to solid-liquid separation by the centrifuge or the decanter, the solid is output to the reaction system, the mother liquor is pumped into a mother liquor tank by a pump, and the mother liquor tank is respectively communicated with a reaction kettle of the urotropine batching tank and a reaction kettle of the chloroacetic acid batching tank by pipelines; the substances in the mother liquor are mainly methanol and a small amount of urotropine, and the methanol is relatively stable in the whole reaction, so that the difference between the quality of the methanol in the mother liquor and the initial methanol input amount is not large; preferably, the mother liquor is filled with two sets of flow meters and valves, and the amount of the mother liquor entering the urotropine batching tank and the chloroacetic acid batching tank is controlled respectively;
(4) the mother liquor separated by the solid-liquid separator is fed back to the urotropine batching tank and the chloroacetic acid batching tank, newly added urotropine solid and chloroacetic acid solid are respectively dissolved, and then the materials in the batching system are pumped into the continuous reactor by a pump through a pipeline to realize continuous reaction.
Further, the mass ratio of the chloroacetic acid solid added in the step (1) to the methanol is as follows: 1.1-1.5: 1, wherein the ratio of the urotropine solid to the methanol is as follows: 0.8-1.2: 1.8-4.3, wherein the mass ratio of the chloroacetic acid solid to the urotropine solid is as follows: 4:1.
Further, in the continuous reaction in the step (4), the mass ratio of chloroacetic acid solid to urotropine solid supplemented to the batching system each time is 12-16: 0.4 to 1.0.
Further, in the continuous reaction in the step (4), the mass ratio of the chloroacetic acid solid to the mother liquor supplemented to the batching system each time is as follows: 3.5-4.8: 2.8-3.3, wherein the mass ratio of the urotropine solid to the mother liquor is as follows: 0.9-1.1: 14-16; the mass ratio of liquid ammonia consumed by each reaction to chloroacetic acid in the continuous reactor is 0.36-0.42: 1.
further, the dissolution of the urotropine solid and the chloroacetic acid solid in the compounding system is carried out at a temperature of 40-60 ℃.
Further, the reaction temperature of the continuous reactor is 60-75 ℃, and the reaction pH is 6.0-8.0.
Compared with the prior art, the method for continuously preparing the glycine in the alcohol phase has the following advantages: the method adopts a tubular reactor or a tower reactor with a certain height-diameter ratio, realizes the high-efficiency circulating continuous production of the glycine by recycling the mother liquor, improves the reaction efficiency, effectively reduces the back mixing phenomenon, stabilizes the product quality, is simple to operate, and is beneficial to the operation of technical personnel.
Detailed Description
The present invention will be described in detail with reference to examples.
The first embodiment is as follows:
dissolving urotropine 3.75kg in methanol 14.0kg in a reaction kettle of a urotropine raw material tank, stirring for 20min, and feeding into a raw material tank of a urotropine batching system; dissolving 15.0kg of chloroacetic acid in 10.0kg of methanol in a reaction kettle of a chloroacetic acid batching system, stirring for 20min, and then feeding the mixture into a stock tank of the chloroacetic acid batching system; putting the urotropine and chloroacetic acid into a tubular reactor according to the ratio of 1:4, and introducing liquid ammonia from the bottom of the tubular reactor, wherein the introduction amount of the liquid ammonia is 6.0 kg; the height of each pipe of the tubular reactor is 1000mm, the effective diameter is 50mm, the reaction temperature of the tubular reactor is 69 ℃, the pH value is 7.2-7.4, and white solids in the tubular reactor gradually increase along with the reaction; after 1h, the reaction is finished, and the reaction product in the tubular reactor is pumped into a centrifuge by a pump, the centrifugal rotation speed is 10000rpm, the centrifugal time is 3min, and finally 37.0kg of mixed crystal is obtained, wherein the mixed crystal is a wet material with 50% of solid content; pumping the mother liquor into a mother liquor tank through a pump, adding 0.8kg of urotropine solid and 14.0kg of mother liquor in a reaction kettle in a urotropine batching system, stirring for 20min, and then feeding into a urotropine raw material tank; putting 15.0kg of chloroacetic acid and 10.0kg of mother liquor in a chloroacetic acid batching system into a reaction kettle, stirring for 20min, then putting the mother liquor into a chloroacetic acid raw material tank, putting urotropine and chloroacetic acid into a tubular reactor according to the ratio of 1:4, and simultaneously introducing liquid ammonia from the bottom of the tubular reactor, wherein the introduction amount of the liquid ammonia is 6.0 kg; and finally obtaining 39.4kg of mixed crystal, wherein the mixed crystal is a wet material with the solid content of 50 percent, and the glycine content is 11.5 kg.
Example two:
dissolving urotropine 3.0kg in methanol 7.50kg in a reaction kettle of a urotropine batching system, stirring for 20min, and feeding into a raw material tank of the urotropine batching system; dissolving 12.0kg of chloroacetic acid in 10.0kg of methanol in a reaction kettle of a chloroacetic acid batching system, stirring for 20min, and then feeding the mixture into a stock tank of the chloroacetic acid batching system; putting urotropine and chloroacetic acid into a tower reactor according to the ratio of 1:4, and introducing liquid ammonia from the bottom of the tower reactor, wherein the introduction amount of the liquid ammonia is 4.8 kg; the height of the tower reactor is 1200mm, the effective diameter is 50mm, the reaction temperature is controlled at 63 ℃, the pH value is 6.1-6.4, and white solids in the tower reactor gradually increase along with the reaction; after 1h, the reaction is finished, and the reaction product in the reactor is pumped into a centrifuge by a pump, wherein the centrifugal speed is 10000rpm, the centrifugal time is 3min, and finally 28.5kg of mixed crystal is obtained, wherein the mixed crystal is a wet material with the solid content of 55%; pumping the mother liquor into a mother liquor tank by a pump. Adding 12.0kg of chloroacetic acid and 0.5kg of urotropine into a chloroacetic acid and urotropine batching system respectively, adding 10.0kg of mother liquor and 7.5kg of mother liquor respectively for dissolving, stirring for 25min, and then feeding into a corresponding raw material tank. Introducing urotropine and chloroacetic acid into a tower reactor according to the ratio of 1:4, and simultaneously introducing liquid ammonia from the bottom of the reactor, wherein the introduction amount of the liquid ammonia is 4.8 kg; 29.65kg of mixed crystal is finally obtained, wherein the mixed crystal is a wet material with the solid content of 55 percent, and the glycine content is 9.5 kg.
Example three:
dissolving urotropine 8.0kg in methanol 28.0kg in a reaction kettle of a urotropine batching system, stirring for 20min, and feeding into a raw material tank of the urotropine batching system; dissolving 32.0kg of chloroacetic acid in 21.5kg of methanol in a reaction kettle of a chloroacetic acid batching system, stirring for 20min, and then feeding the mixture into a raw material tank of the chloroacetic acid batching system; introducing urotropine and chloroacetic acid into a tower reactor according to the ratio of 1:4, and simultaneously introducing liquid ammonia from the bottom of the tower reactor, wherein the introduction amount of the liquid ammonia is 13.0 kg; the height of the tower reactor is 1600mm, the effective diameter is 75mm, the reaction temperature is controlled at 68 ℃, the pH value is 6.2-6.6, and white solids in the tower reactor gradually increase along with the reaction; after 1h, the reaction is finished, and the reaction product in the reactor is pumped into a centrifuge at the centrifugal speed of 15000rpm for 5min to finally obtain 50.2kg of wet material mixed crystal with the solid content of 82%; pumping the mother liquor into a mother liquor tank by a pump. When the chloroacetic acid is used for mixing, 32.0kg of chloroacetic acid and 21.5kg of mother liquor are added, stirred for 30min and then enter a chloroacetic acid raw material tank; when urotropine is prepared, adding 2.0kg of urotropine and 28.0kg of mother liquor, stirring for 30min, and then feeding into a urotropine raw material tank; then, feeding the urotropine and chloroacetic acid into a tower reactor according to the ratio of 1:4, and simultaneously introducing liquid ammonia from the bottom of the reactor, wherein the introduction amount of the liquid ammonia is 13.0 kg; finally, 52.2kg of mixed crystal with the solid content of 82 percent is obtained, wherein the glycine content is 25.0 kg.
Comparative example one:
when the chloroacetic acid is used for mixing, 32.0kg of chloroacetic acid and 21.5kg of methanol are added, stirred for 30min and then enter a chloroacetic acid raw material tank; when urotropine is prepared, adding 8.0kg of urotropine and 28.0kg of methanol, stirring for 30min, and then feeding into a urotropine raw material tank; chloroacetic acid and urotropine enter a tower reactor according to the ratio of 4:1 to react with liquid ammonia, the height of the tower reactor is 800mm, the effective diameter is 60mm, and the height-diameter ratio is 13.3; controlling the reaction temperature to be 68 ℃ and the pH value to be 6.2-6.6, gradually increasing white solids in the reactor along with the reaction, pumping the product after the reaction into a subsequent centrifuge from a discharge hole of the reactor through a pump, and returning the mother liquor after centrifugal separation to a batching system. Only 35.6kg of wet mixed crystals with a solids content of 82% were finally obtained by means of a solid-liquid separator, the glycine content being 17.0 kg. Compared with the three phases of the embodiment, the reactor has smaller height-diameter ratio and shorter reaction residence time, and the obtained mixed crystals are obviously smaller.
Comparative example two:
when the chloroacetic acid is used for mixing, 32.0kg of chloroacetic acid and 21.5kg of methanol are added, stirred for 30min and then enter a chloroacetic acid raw material tank; when urotropine is prepared, adding 8.0kg of urotropine and 28.0kg of methanol, stirring for 30min, and then feeding into a urotropine raw material tank; putting two materials of chloroacetic acid and urotropine into a tower reactor according to the proportion of 4:1 to react with ammonia, wherein the height of the tower reactor is 1200mm, the effective diameter is 40mm, and the height-diameter ratio is 30; the reaction temperature is controlled to be 68 ℃, the pH value is 6.2-6.6, white solids are gradually increased along with the reaction, and finally, the pump is blocked due to too high solid content at the bottom of the reactor, so that stable discharging cannot be realized. Compared with the three phases of the examples, the reaction conversion rate is too high due to the larger height-diameter ratio of the reactor, so that solid is accumulated and stable discharge is not facilitated.
Comparative example three:
putting 8.0kg of urotropin and 28.0kg of methanol into a reaction kettle, and heating to 68 ℃; dissolving 32.0kg of chloroacetic acid in 21.5kg of methanol, adding the solution into a reaction kettle by a pump, and controlling the temperature of reaction liquid in the kettle to be 68 ℃ and the pH value to be 6.2-6.6; the addition was completed for 1h and the reaction was continued for 1 h. After the reaction, 48.2kg of mixed crystals with 82% of solid content is obtained through a solid-liquid separator, wherein the glycine content is 23.1 kg. Compared with the three phases of the examples, the yield is not high even if the reaction time is prolonged due to the problems of material back mixing and the like in the reaction kettle.
The first embodiment, the second embodiment and the third embodiment and the first comparative embodiment, the second comparative embodiment and the third comparative embodiment show that the tubular reactor or the tower reactor with a certain height-diameter ratio is adopted, the efficient circulating continuous production of the glycine is realized, the reaction efficiency is improved, the back mixing phenomenon is effectively reduced, and the product quality is stabilized.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A method for continuously preparing glycine in an alcohol phase is characterized in that: the system comprises the following systems: a batching system, a continuous reactor and a solid-liquid separator; the batching system, the continuous reactor and the solid-liquid separator are communicated in sequence, and mother liquor separated by the solid-liquid separator returns to the batching system; the batching system comprises a urotropine batching tank and a chloroacetic acid batching tank, wherein the urotropine batching tank and the chloroacetic acid batching tank are respectively connected with the continuous reactor through pipelines, and the continuous reactor is a tube-type reactor or a tower-type reactor.
2. The method for continuously preparing glycine in alcohol phase according to claim 1, wherein: the height-diameter ratio of each pipe in the tubular reactor is 20-30: 1.
3. the method for continuously preparing glycine in alcohol phase according to claim 1, wherein: the height-diameter ratio of the tower reactor is 15-25: 1.
4. the method for continuously preparing glycine in alcohol phase according to claim 1, wherein: the preparation method comprises the following steps:
(1) dissolving urotropine solid and chloroacetic acid solid in a urotropine mixing tank and a chloroacetic acid mixing tank respectively by using methanol;
(2) materials in the urotropine batching tank and the chloroacetic acid batching tank are pumped into the continuous reactor from the top of the continuous reactor, and liquid ammonia is pumped into the continuous reactor from the bottom of the continuous reactor;
(3) the lower half part of the continuous reactor is provided with a discharge hole, and the reacted materials in the continuous reactor are pumped into a solid-liquid separator to realize solid-liquid separation in the solid-liquid separator;
(4) and (3) inputting the mother liquor separated by the solid-liquid separator back into a urotropine mixing tank and a chloroacetic acid mixing tank, respectively dissolving newly added urotropine solid and chloroacetic acid solid, and then pumping the dissolved materials into a continuous reactor to realize continuous reaction.
5. The method for continuously preparing glycine in alcohol phase according to claim 4, wherein: the mass ratio of the chloroacetic acid solid to the methanol added in the step (1) is as follows: 1.1-1.5: 1, wherein the ratio of the urotropine solid to the methanol is as follows: 0.8-1.2: 1.8-4.3, wherein the mass ratio of the chloroacetic acid solid to the urotropine solid is as follows: 4:1.
6. The method for continuously preparing glycine in alcohol phase according to claim 4, wherein: in the continuous reaction in the step (4), the mass ratio of chloroacetic acid solid to urotropine solid supplemented to the batching system is 12-16: 0.4 to 1.0.
7. The method for continuously preparing glycine in alcohol phase according to claim 4, wherein: in the continuous reaction in the step (4), the mass ratio of chloroacetic acid solid to mother liquor supplemented to the batching system each time is as follows: 3.5-4.8: 2.8-3.3, wherein the mass ratio of the urotropine solid to the mother liquor is as follows: 0.9-1.1: 14 to 16.
8. The method for continuously preparing glycine in alcohol phase according to claim 4, wherein: the solid urotropine and the solid chloroacetic acid are dissolved at the temperature of 40-60 ℃.
9. The method for continuously preparing glycine in alcohol phase according to claim 4, wherein: the reaction temperature of the continuous reactor is 60-75 ℃, and the reaction PH is 6.0-8.0.
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Cited By (1)
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| CN112409177A (en) * | 2020-11-26 | 2021-02-26 | 中国天辰工程有限公司 | Method for continuously producing 1, 4-cyclohexane dimethyl phthalate |
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