CN109836344B - Method for producing glycine by organic solvent - Google Patents
Method for producing glycine by organic solvent Download PDFInfo
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- CN109836344B CN109836344B CN201711199327.6A CN201711199327A CN109836344B CN 109836344 B CN109836344 B CN 109836344B CN 201711199327 A CN201711199327 A CN 201711199327A CN 109836344 B CN109836344 B CN 109836344B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
Abstract
A method for producing glycine and co-producing ammonium chloride by using an organic solvent. The organic solvent comprises the following components: ethylene glycol, propylene glycol, Dimethylacetamide (DMAC), and methanol and ethanol that can be compounded into the above solvents. Adding reaction organic solvent into a reactor for producing glycine, adding catalyst urotropine, adding chloroacetic acid, introducing ammonia to synthesize glycine. Cooling, filtering, washing and drying to obtain the glycine product. And (3) adding chloroacetic acid or ammonium chloroacetate into the organic solvent, precipitating ammonium chloride to crystallize, washing and drying to obtain an ammonium chloride product. The organic solvent is recycled.
Description
Technical Field
The invention relates to a clean production process of glycine, which utilizes an organic solvent to produce glycine and belongs to the technical field of chemical production.
Background
The glycine is an important raw material of products such as glyphosate, glycine ethyl ester hydrochloride and the like, and can also be refined into food-grade glycine for use. The domestic traditional glycine production process by chloroacetic acid amino hydrolysis method comprises the following steps: adding an aqueous solution containing about 25% of catalyst urotropine into a reaction kettle filled with cooling water, simultaneously dropwise adding an aqueous solution containing about 80% of chloroacetic acid and introducing liquid ammonia, and carrying out ammonolysis reaction at the conditions of about pH 7 and reaction temperature of about 70-80 ℃. And separating the ammonolysis reaction liquid containing the glycine and the ammonium chloride obtained after the reaction by using a methanol-alcohol precipitation method to obtain a glycine product. The production of one ton of glycine is to produce about 12-13 cubic meters of mother liquor containing methanol, wherein the mother liquor of methanol contains about 5 percent of ammonium chloride, about 1 percent of urotropine and about 0.8 percent of glycine. About 5 tons of steam is consumed for recycling the methanol when one ton of glycine is produced, and about 150 kilograms of urotropine is consumed for producing one ton of glycine, so that the urotropine cannot be recycled. 60-100 kg of methanol is also consumed for the production of one ton of glycine. Rectifying the methanol mother liquor to recover methanol to obtain dealcoholized wastewater. The dealcoholized wastewater is evaporated and concentrated to obtain a byproduct ammonium chloride which is used for producing chemical fertilizers. The black wastewater containing a large amount of urotropine, glycine and other organic matters left after the ammonium chloride byproduct is recovered is very difficult to treat, so that the environment is polluted, and precious resources are wasted.
In patents US5155264 and CN1080632, chloroacetic acid and ammonia are used as raw materials, and glycine can be separated in the presence of a catalyst and organic amine, but the catalyst and organic amine in the mother liquor are not recycled. Patent CN101270061 uses chloroacetic acid and ammonia as raw materials, glycine can be separated out in the presence of urotropine and organic amine, but a large amount of sodium alkoxide or potassium alkoxide needs to be consumed, which is high in cost and has no value in industrial production. In patent CN102030669, chloroacetic acid and ammonia are used as raw materials, and organic amine is used as an acid-binding agent under the action of a catalyst, so that separation of glycine and ammonium chloride can be realized. However, the process is complex and the reaction end point is difficult to control. When the triethylamine hydrochloride is recovered by ammonia, the triethylamine can not be completely recovered, and a small amount of mixed crystals of glycine and ammonium chloride are generated in the production process, and further separation is needed.
The present applicant of the present invention, CN104478747 (a method for producing glycine using an organic solvent), produces glycine using a glycol solvent or a glycol derivative solvent and methanol (or ethanol) as a mixed organic solvent. Adding organic solvent and catalyst urotropine into a reactor for producing glycine, adding chloroacetic acid, and slowly introducing ammonia to synthesize glycine. After the reaction is finished, glycine crystals are filtered out at the temperature of 50-75 ℃. Freezing and cooling the filtrate to obtain the side product ammonium chloride.
The process utilizes the different solubility of ammonium chloride in organic solvent under different temperature conditions to obtain a byproduct ammonium chloride by a freezing and cooling mode. The disadvantage of this method is that the yield of ammonium chloride as a byproduct obtained each time is limited, and the yield of glycine single-kettle production is also influenced. In order to obtain ammonium chloride as a byproduct as much as possible in single-kettle production, the organic solvent needs to be cooled by freezing, so that the energy consumption is relatively high.
Disclosure of Invention
The invention provides a clean production process of glycine, which utilizes an organic solvent to produce glycine and coproduces an ammonium chloride product. The organic solvent used in the present invention includes the following: ethylene glycol, propylene glycol, Dimethylacetamide (DMAC), and methanol and ethanol that can be compounded into the above solvents. The solvent used in the invention can be one of ethylene glycol, propylene glycol and Dimethylacetamide (DMAC) solvent, and can also be an organic solvent formed by mixing one of the above solvents with methanol (or ethanol). Or several of ethylene glycol, propylene glycol and Dimethylacetamide (DMAC) solvent mixed with methanol or ethanol. In the organic solvent, the weight percentage of methanol (or ethanol) in the organic solvent is as follows: 1 to 40 percent.
The invention is realized by the following steps and methods:
step (1), synthesizing glycine from chloroacetic acid in an organic solvent: adding a reaction organic solvent (ethylene glycol, propylene glycol, Dimethylacetamide (DMAC) solvent or a compound organic solvent) into a reactor for producing glycine (a condenser is arranged above the reactor and is connected with a solvent condensation reflux device and a solvent condensation recovery device), adding a catalyst urotropine, then adding chloroacetic acid, and then slowly introducing ammonia to carry out a reaction for synthesizing glycine. The temperature is controlled between 40 ℃ and 75 ℃. The ammonia introduction time is controlled between 0.5 and 2 hours, when the pH value of the solvent reaches 7 to 7.5, the ammonia introduction is stopped, and the reaction is carried out for 0.1 to 1 hour under the condition of heat preservation. The mol ratio of the chloroacetic acid to the ammonia is 1: 2-3. The amount of the organic solvent is 3 to 12 times of the weight of the added chloroacetic acid. The amount of the catalyst urotropin added is 0.1-7 wt% of the organic solvent. After the reaction is finished, filtering out crude glycine crystals from the reaction solution at the temperature of 35-55 ℃ to obtain a circulating reaction organic solvent filtrate. And washing, centrifuging and drying the crude glycine product by using methanol to obtain the glycine product.
The chloroacetic acid raw material can be added in the steps to be changed into ammonium chloroacetate (the ammonium chloroacetate is solid obtained by cooling, crystallizing and centrifuging after the chloroacetic acid is dissolved in water and ammonia is introduced to the pH value of 6) raw material to be subjected to the reaction for synthesizing the glycine. Adding ammonium chloroacetate into an organic solvent, introducing ammonia for 0.5-2 hours at 40-75 ℃, stopping introducing ammonia when the pH value of the solvent reaches 7-7.5, and keeping the temperature for reaction for 0.1-1 hour. The mol ratio of ammonium chloroacetate to ammonia is 1: 1-2.
Step (2), producing a byproduct ammonium chloride:
centrifugally separating the cyclic reaction organic solvent obtained by the crude glycine, adding chloroacetic acid (or adding ammonium chloroacetate), cooling to 10-35 ℃, and centrifugally obtaining crude ammonium chloride and the cyclic reaction organic solvent containing chloroacetic acid (or ammonium chloroacetate). Because the solubility of chloroacetic acid and ammonium chloroacetate in the circulating reaction organic solvent is higher than that of ammonium chloride, the solubility of ammonium chloride in the organic solvent can be reduced after the chloroacetic acid or the ammonium chloroacetate is added, and a large amount of ammonium chloride is separated out and crystallized. Washing the centrifuged crude ammonium chloride with methanol, and drying to obtain an ammonium chloride product. The methanol of the ammonium chloride is washed, and the chloroacetic acid (or ammonium chloroacetate) washed in the methanol is recovered after the methanol is distilled. The dosage of chloroacetic acid or ammonium chloroacetate in the production of ammonium chloride is the same as the dosage of glycine synthesized in the step (1).
Step (3), synthesizing glycine by circularly reacting an organic solvent:
crystallizing and separating out the circulating reaction organic solvent (containing chloroacetic acid or ammonium chloroacetate) of ammonium chloride, adding a small amount of catalyst urotropine, introducing ammonia to perform glycine synthesis reaction, controlling the time of introducing ammonia to be between 0.5 and 2 hours, controlling the temperature to be between 40 and 75 ℃, stopping introducing ammonia when the pH value of the solvent reaches 7 to 7.5, and keeping the temperature for reaction for 0.1 to 1 hour. After the reaction is finished, filtering out crude glycine crystals by using the reaction solvent at the temperature of between 35 and 55 ℃, and simultaneously obtaining the filtrate of the organic solvent for the cyclic reaction. And washing, centrifuging and drying the crude glycine product by using methanol to obtain the glycine product. And (3) sending the organic solvent of the circular reaction into the process for producing ammonium chloride in the step (2).
And (4) recycling the organic solvent of the cyclic reaction:
after the organic solvent of the circular reaction is reacted for 10 to 40 times, the color becomes dark due to impurity enrichment, and the organic solvent needs to be recycled. The organic solvent can be recovered by adopting the modes of membrane separation, reduced pressure distillation and rectification. The remaining colored substances (main components: ammonium chloride, urotropine, glycine, reaction byproducts and the like) are firstly subjected to catalytic oxidation treatment and then dried and processed into chemical fertilizer raw material products. Or the residual colored substances are sent to the conventional wastewater treatment process for wastewater treatment after catalytic oxidation.
The specific implementation mode is as follows: the following examples are provided to further illustrate the essence of the present invention, but are not intended to limit the present invention.
The first embodiment is as follows: 600 ml of organic solvent (wherein the methanol is 100 ml, the ethylene glycol is 300 ml, and the Dimethylacetamide (DMAC) is 200 ml) and 95g of chloroacetic acid are compounded, 30g of urotropine is put into a four-neck flask which is provided with a stirrer, a thermometer, a reflux condenser and a water bath for cooling, stirred and dissolved, the temperature is kept below 45 ℃, and 17g of liquid ammonia is introduced within one hour. Then, ammonia is continuously introduced, the temperature is controlled between 50 ℃ and 65 ℃, 25g of ammonia is introduced within 1 hour, and the reaction is stopped until the pH value reaches 7.5. And (3) cooling to 40 ℃, filtering to obtain crude glycine crystals, washing with methanol, filtering and drying to obtain 70.72g of glycine with the content of 98.16%.
And (3) adding 95g of chloroacetic acid into the filtered cyclic reaction organic solvent in batches, cooling to 20 ℃, and filtering out an ammonium chloride crude product and the cyclic reaction organic solvent containing chloroacetic acid. The crude ammonium chloride was washed with methanol, filtered and dried to give 37.71g of ammonium chloride.
Example two: the organic solvent for the cyclic reaction containing chloroacetic acid obtained in example one was charged into a four-necked flask, and reacted with ammonia. The temperature was kept below 45 ℃ and 17g of liquid ammonia was introduced over one hour. Then, ammonia is continuously introduced, the temperature is controlled between 50 ℃ and 65 ℃, 26g of ammonia is introduced within 1 hour, and the reaction is stopped until the pH value reaches 7.3. And (3) cooling to 40 ℃, filtering to obtain crude glycine crystals, washing with methanol, filtering and drying to obtain 73.51g of glycine with the content of 98.43%.
And (3) adding 95g of chloroacetic acid into the filtered cyclic reaction organic solvent in batches, cooling to 20 ℃, and filtering out an ammonium chloride crude product and the cyclic reaction organic solvent containing chloroacetic acid. The crude ammonium chloride was washed with methanol, filtered and dried to obtain 52.17g of ammonium chloride.
Example three: mixing 600 ml of organic solvent (100 ml of methanol, 250ml of ethylene glycol, 250ml of Dimethylacetamide (DMAC)) and 112g of ammonium chloroacetate, and 30g of urotropine are put into a four-neck flask with a stirrer, a thermometer, a reflux condenser and a water bath for cooling, stirred and dissolved, the temperature is controlled between 50 ℃ and 65 ℃, 25g of ammonia is introduced within 1 hour, and the reaction is stopped until the PH value reaches 7.3. And (3) cooling to 40 ℃, filtering to obtain crude glycine crystals, washing with methanol, filtering and drying to obtain 72.37g of glycine with the content of 98.35%.
And (3) adding 112g of ammonium chloroacetate into the filtered cyclic reaction organic solvent in batches, cooling to 20 ℃, and filtering to obtain an ammonium chloride crude product and the cyclic reaction organic solvent containing the ammonium chloroacetate. The crude ammonium chloride was washed with methanol, filtered and dried to obtain 35.47g of ammonium chloride.
Example four: the organic solvent of the cyclic reaction containing ammonium chloroacetate obtained in example three was added to a four-neck flask and reacted with ammonia. The temperature is controlled between 50 ℃ and 65 ℃, 26g of ammonia is introduced within 1 hour, and the reaction is stopped until the pH value reaches 7.4. And (3) cooling to 40 ℃, filtering to obtain crude glycine crystals, washing with methanol, filtering and drying to obtain 73.21g of glycine with the content of 98.49%.
And (3) adding 112g of ammonium chloroacetate into the filtered cyclic reaction organic solvent in batches, cooling to 20 ℃, and filtering to obtain an ammonium chloride crude product and the cyclic reaction organic solvent containing the ammonium chloroacetate. The crude ammonium chloride was washed with methanol, filtered and dried to obtain 54.16g of ammonium chloride.
Claims (5)
1. A method for producing glycine by using organic solvent, which respectively uses ethylene glycol, propylene glycol and Dimethylacetamide (DMAC) as organic solvent, or methanol or ethanol is mixed in the above solvents as organic solvent, or several of ethylene glycol, propylene glycol and Dimethylacetamide (DMAC) solvents and methanol or ethanol are mixed together to form the organic solvent for synthesizing glycine, and can co-produce ammonium chloride while producing glycine, characterized in that the method comprises the following steps:
(1) adding organic solvent and catalyst urotropine into a reactor for producing glycine, adding chloroacetic acid or adding solid ammonium chloroacetate, and then slowly introducing ammonia;
(2) after the reaction is finished, cooling to 35-55 ℃, filtering out crude glycine crystals, washing with methanol or ethanol, filtering and drying to obtain a glycine product;
(3) adding chloroacetic acid or ammonium chloroacetate into the filtered cyclic reaction organic solvent, wherein the adding amount of chloroacetic acid or ammonium chloroacetate is the same as that of glycine synthesis, cooling to 10-35 ℃, and centrifuging to obtain crude ammonium chloride and a cyclic reaction organic solvent containing chloroacetic acid or ammonium chloroacetate;
(4) washing the crude ammonium chloride with methanol or ethanol, and drying to obtain an ammonium chloride product;
(5) introducing ammonia into a cyclic reaction organic solvent containing chloroacetic acid or ammonium chloroacetate to perform glycine synthesis reaction, cooling, filtering and washing to obtain a glycine product;
(6) and (3) filtering out the cyclic reaction organic solvent, adding chloroacetic acid or ammonium chloroacetate, cooling, crystallizing, filtering, washing and drying to obtain an ammonium chloride product.
2. The method of claim 1, wherein: the organic solvent in the step (1) comprises ethylene glycol, propylene glycol and Dimethylacetamide (DMAC).
3. The method of claim 1, wherein: in the organic solvent in the step (1), the weight percentage of methanol or ethanol in the mixed solvent is as follows: 0.1 to 40 percent.
4. The method of claim 1, wherein: and (3) adding chloroacetic acid into the filtered glycine circulating reaction organic solvent, and separating out crystals to obtain an ammonium chloride product.
5. The method of claim 1, wherein: and (4) adding ammonium chloroacetate into the filtered glycine cyclic reaction organic solvent, and separating out crystals to obtain an ammonium chloride product.
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| CN104478747B (en) * | 2015-01-07 | 2016-04-27 | 刘长飞 | A kind of method utilizing organic solvent to produce glycine |
| CN105859571A (en) * | 2015-01-19 | 2016-08-17 | 刘长飞 | Method for producing glycine by mixed solvent method |
| CN106699591A (en) * | 2015-11-16 | 2017-05-24 | 青岛森美克化工技术有限公司 | Clean production process of glycine and co-produced ammonium chloride |
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