CN108558687B - Method for catalytically synthesizing glycine in homogeneous system - Google Patents
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- 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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- C01C1/164—Ammonium chloride
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Abstract
The invention discloses a method for catalytically synthesizing glycine in a homogeneous system, which takes chloroacetic acid and ammonia gas as raw materials, carries out ammonolysis reaction in the presence of a substituted pyridine catalyst and a solvent, and respectively obtains glycine and ammonium chloride after the operations of filtering, washing and the like on reaction liquid obtained by the ammonolysis reaction.
Description
Technical Field
The invention relates to a method for catalytically synthesizing glycine in a homogeneous system, in particular to a novel method for synthesizing glycine in a homogeneous system, and belongs to the technical field of chemical synthesis.
Background
Glycine, also known as aminoacetic acid, of formula C2H5NO2Structural formula NH2CH2COOH, molecular weight 75.07. Glycine is a white monoclinic or hexagonal crystal or white crystalline powder, and is the amino acid with the smallest molecular weight and the simplest structure. Glycine is used as an important fine chemical intermediate and is widely applied to the fields of pesticides, medicines, foods, feeds, electroplating, organic synthesis and the like. In the aspect of pesticides, glycine can be used for preparing herbicide glyphosate and plant growth regulator glyphosate; in medicine, glycine can be used in various amino acid infusion formulations, chlortetracycline buffer, L-dopa and some important amino groupsAcid intermediates and the like; in food aspect, it can be used as food additive, beverage debitterizing agent, food antioxidant, etc.; in addition, the glycine is widely applied to feed additives, organic solvents and daily chemical products, and is a very important chemical.
The existing glycine synthesis method mainly comprises a chloroacetic acid ammonolysis process, a Strecker process, a Hydantion process, a biological process and the like. The yield is the largest, the most common is the chloroacetic acid ammonolysis process, and the domestic traditional glycine production process by the chloroacetic acid ammonolysis process is as follows: adding an aqueous solution containing 25% of catalyst urotropine into a reaction kettle filled with cooling water, simultaneously dropwise adding an aqueous solution containing about 70% of chloroacetic acid and introducing liquid ammonia, and carrying out ammonolysis reaction at the conditions of about pH value 7 and reaction temperature of about 80 ℃. And (3) carrying out methanol-alcohol separation on the ammonolysis reaction liquid containing the glycine and the ammonium chloride obtained after the reaction is finished to obtain a glycine product. About 12-13 cubic methanol mother liquor is produced for producing 1 ton of glycine, wherein the methanol mother liquor 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 recovering methanol when one ton of glycine is produced, and about 150kg of urotropine is consumed for producing one ton of glycine, so that the urotropine cannot be recycled. 60-100kg 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 fertilizer, and the black wastewater containing a large amount of urotropine, glycine and other organic matters left after the byproduct ammonium chloride is recovered is difficult to treat, so that the environment is polluted, and precious resources are wasted.
In the prior art, for example, patent documents US3215736, US3510515, CN1058957, CN1136035, CN1340498, CN1803763 and CN1896049, etc. all report technical schemes for preparing glycine by using chloroacetic acid as a raw material, urotropine as a catalyst and water as a solvent. The method for producing glycine containing aqueous phase has the problems of unrecoverable catalyst, high catalyst consumption, low catalytic efficiency, unrecovered raw materials, and the like, and is easy to generate hydrolysate glycolic acid due to strong alkalinity, water content and the like of a system, thereby causing waste and environmental pollution; in addition, there are disadvantages that separation of inorganic salts such as ammonium chloride generated during the reaction is difficult, the amount of post-treatment is large, and judgment of the end point of the synthesis reaction is difficult.
In order to solve the technical defect of the prior art that the urotropine is used as a catalyst to prepare the glycine, the prior art provides the following improvement scheme:
(1) in the method, an alcohol phase solvent is used in the reaction process, as reported in patent document CN1410417, chloroacetic acid and ammonia are used as raw materials, urotropine is used as a catalyst, and the solvent is used as an alcohol phase, and the method is used for preparing glycine by introducing ammonia gas into an alcohol phase for reaction.
(2) In the reaction process, organic amine is added, and as reported in patent documents U.S. Pat. Nos. 5155264 and CN1080632, chloroacetic acid and ammonia are used as raw materials, glycine can be separated in the presence of a catalyst and the organic amine, but the catalyst and the organic amine in the mother liquor are not recycled. And patent document CN101270061 reports that chloroacetic acid and ammonia are used as raw materials, glycine can be separated and removed in the presence of urotropine and organic amine, but a large amount of sodium alkoxide and potassium alkoxide are consumed, the cost is high, and no industrial production value exists.
(3) The method for producing glycine by carrying out aminolysis reaction in a homogeneous system by using ionic liquid as a catalyst and chloroacetic acid and ammonia gas as reaction raw materials, as reported in patent document CN107216262, uses the ionic liquid as a catalyst instead of urotropine, and on one hand, adopts the ionic liquid suitable for a water phase system, but the ionic liquid needs special customization and is expensive, and on the other hand, the process production is complex and is not beneficial to industrial production.
In the existing glycine synthesis method, due to the problems of difficult separation of inorganic salts such as ammonium chloride and the like, large post-treatment capacity, difficult judgment of synthesis reaction end point and the like, the following improvement scheme is provided in the prior art:
(1) patent document CN104418759 reportsThe method for preparing glycine by alcohol phase synthesis, chromatographic separation and MVR evaporative crystallization overcomes the trouble of inorganic salt subsequent treatment in the alcohol phase reaction process, can realize effective separation of glycine and ammonium chloride by adopting the modes of chromatographic separation and MVR evaporative crystallization, and can realize that the glycine content can reach 99.6 percent and cl is-Less than or equal to 0.3 percent, the content of ammonium chloride in the ammonium chloride product is more than 99 percent, the content of iron ions is less than or equal to 0.002 percent, and the total yield of glycine is more than or equal to 94 percent. However, in actual production, the chromatographic separation treatment cost is high.
(2) Patent document CN1340498 reports that for the dissolution of chloroacetic acid and ammonia after liquid phase reaction, crystallization separation and alcohol-water mixed dissolution separation of ammonium chloride are adopted, and the mother liquor from which ammonium chloride is taken out is mixed with the removed alcohol for recycling, so that the method has the purposes of improving product yield and reducing waste brine discharge. The content of glycine can reach 99.2%, cl-Less than or equal to 0.53 percent and the total yield of the glycine is more than or equal to 95.94 percent. Because the ammonium chloride is separated by adopting the alcohol-water mixed dissolution method, wastewater is discharged in the actual production process, and the environmental protection pressure of subsequent wastewater treatment is increased.
Disclosure of Invention
The invention aims to provide a method for catalytically synthesizing glycine in a homogeneous system, which is characterized in that substituted pyridine is added into a reaction system as a catalyst to synthesize the glycine, so that the problems of low catalytic efficiency, easy loss of the catalyst, serious side reaction and the like of urotropine can be effectively solved, and the method has the advantages of high conversion rate, easy purification of products, difficult loss of the catalyst, recycling and the like. The method reduces production cost and pollution, and has high practical value.
The invention is realized by the following technical scheme: a method for catalytically synthesizing glycine in a homogeneous system comprises the following steps:
a: taking chloroacetic acid and ammonia gas as raw materials, and carrying out ammonolysis reaction in the presence of a substituted pyridine catalyst and a solvent;
b: filtering the reaction liquid obtained by the ammonolysis reaction in the step A, washing a filter cake to obtain a product glycine, and filtering mother liquor to perform the operation in the step C;
c: cooling and filtering the filtered mother liquor obtained in the step B to obtain mixed crystal solid containing ammonium chloride and glycine, and recycling the filtered filtrate to the step A;
d: and D, washing, filtering and drying the mixed crystal solid obtained in the step C to obtain an ammonium chloride product.
In the step A, the substituted pyridine catalyst is selected from one of 3, 5-lutidine, 2, 4-lutidine, 4-picoline, 2-picoline and 4-dimethylaminopyridine.
In the step A, the solvent is selected from one or more of methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, ethylene glycol, propylene glycol and butanediol.
In the step A, the mol ratio of chloroacetic acid, ammonia gas and substituted pyridine catalyst is 1: 2.0-2.5: 0.01 to 0.05.
In the step A, the weight of the solvent is 2-8 times of that of chloroacetic acid.
And in the step A, adding perchloroacetic acid, a substituted pyridine catalyst and a solvent into a reactor with reflux condensation and stirring, stirring and mixing for 10-30 min, controlling the temperature of a reaction system to be 60-65 ℃, introducing ammonia gas into the reactor, and stopping the ammonia introduction reaction after the chloroacetic acid peak disappears through liquid chromatography monitoring reaction.
And in the step B, cooling the reaction liquid obtained by the ammonolysis reaction in the step A to 40-45 ℃, filtering, washing a filter cake by methanol or ethanol, and drying to obtain a product glycine.
In the step C, the temperature of the cooled filtrate is-20-10 ℃.
In the step D, washing the mixed crystal solid obtained in the step C with methanol or ethanol, washing with water, filtering and drying to obtain an ammonium chloride product, sending a washing liquid obtained after washing with methanol or ethanol to the step B, and mixing the washing liquid with the washing liquid obtained after washing with methanol or ethanol in the step B for centralized treatment; and (3) recycling the washing liquid after water washing for water washing, and returning the washing liquid to the methanol or ethanol washing step when the concentration of glycine in the washing liquid after water washing is more than 20%.
In the methanol or ethanol washing process, after the solvent is recovered by rectifying the washing liquid, the residual water solution is sent to the water washing process.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) in the method, alcohol solutions such as methanol, ethanol, isopropanol, n-propanol and the like are used as solvents, and substituted pyridine catalysts are used for replacing the existing urotropine catalysts, so that the reaction raw materials are subjected to ammonolysis reaction in an alcohol homogeneous system.
(2) In the method, the dosage of the substituted pyridine catalyst and the solvent is reasonably controlled, and the molar ratio of the chloroacetic acid, the ammonia gas and the substituted pyridine catalyst is controlled to be 1: 2.0-2.5: 0.01-0.05, solvent weight control is 2-8 times of chloroacetic acid weight, in the actual production process, in the alcohol phase system that the solvent provided, only need the quantity of a small amount of substitution pyridine catalyst, can reach effectual catalytic effect, the manufacturing cost of reasonable control, the control of solvent quantity can also improve the precipitation of glycine, avoids ammonium chloride to precipitate and increases the subsequent processing degree of difficulty.
(3) In the method, in the reaction process, through continuous control of a series of operations such as temperature control, reaction raw material addition, liquid chromatography monitoring and the like (for example, ammonia gas is introduced when the temperature of a reaction system is controlled to be 60-65 ℃, reaction liquid is filtered when cooled to 40-45 ℃, the temperature of the cooled filtrate is controlled to be-20-10 ℃, and the like), the production efficiency of glycine is further improved, the precipitation of ammonium chloride and the generation of corresponding side reaction products are reduced, and a foundation is laid for the recycling and zero emission of subsequent mother liquor.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
this example presents a method for the catalytic synthesis of glycine in a homogeneous system. The method comprises the following specific steps:
a: chloroacetic acid and ammonia gas are used as raw materials, and ammonolysis reaction is carried out in the presence of a substituted pyridine catalyst (3, 5-dimethylpyridine) and a solvent (methanol, ethanol and isopropanol).
B: and C, filtering the reaction liquid obtained by the ammonolysis reaction in the step A, washing a filter cake to obtain a product glycine, and filtering mother liquor to perform the operation in the step C.
C: and D, cooling and filtering the filtered mother liquor obtained in the step B to obtain mixed crystal solid containing ammonium chloride and glycine, and recycling the filtered filtrate to the step A.
D: and D, washing, filtering and drying the mixed crystal solid obtained in the step C to obtain an ammonium chloride product.
Example 2:
this example presents a method for the catalytic synthesis of glycine in a homogeneous system. The method comprises the following specific steps:
a: using chloroacetic acid and ammonia gas as raw materials, carrying out ammonolysis reaction in the presence of a substituted pyridine catalyst (2, 4-dimethylpyridine) and a solvent (methanol), and controlling the molar ratio of the chloroacetic acid to the ammonia gas to the 2, 4-dimethylpyridine to be 1: 2.5: 0.05, the weight of the methanol is 2 times of that of the chloroacetic acid.
B: and C, filtering the reaction liquid obtained by the ammonolysis reaction in the step A, washing a filter cake to obtain a product glycine, and filtering mother liquor to perform the operation in the step C.
C: and D, cooling and filtering the filtered mother liquor obtained in the step B to obtain mixed crystal solid containing ammonium chloride and glycine, and recycling the filtered filtrate to the step A.
D: and D, washing, filtering and drying the mixed crystal solid obtained in the step C to obtain an ammonium chloride product.
Example 3:
this example presents a method for the catalytic synthesis of glycine in a homogeneous system. The method comprises the following specific steps:
a: using chloroacetic acid and ammonia gas as raw materials, carrying out ammonolysis reaction in the presence of a substituted pyridine catalyst (4-methylpyridine) and a solvent (ethanol and ethylene glycol), and controlling the molar ratio of the chloroacetic acid to the ammonia gas to the 4-methylpyridine to be 1: 2.0: 0.01, the weight of ethanol and glycol is 8 times of that of chloroacetic acid.
B: and C, filtering the reaction liquid obtained by the ammonolysis reaction in the step A, washing a filter cake to obtain a product glycine, and filtering mother liquor to perform the operation in the step C.
C: and D, cooling and filtering the filtered mother liquor obtained in the step B to obtain mixed crystal solid containing ammonium chloride and glycine, and recycling the filtered filtrate to the step A.
D: and D, washing, filtering and drying the mixed crystal solid obtained in the step C to obtain an ammonium chloride product.
Example 4:
this example presents a method for the catalytic synthesis of glycine in a homogeneous system. The method comprises the following specific steps:
a: using chloroacetic acid and ammonia gas as raw materials, carrying out ammonolysis reaction in the presence of a substituted pyridine catalyst (4-dimethylaminopyridine) and a solvent (methanol and n-propanol), adding perchloroacetic acid, 4-dimethylaminopyridine, methanol and n-propanol into a reactor with reflux condensation and stirring during production, stirring and mixing for 10min, controlling the temperature of a reaction system to be 60-65 ℃, introducing ammonia gas into the reactor, and stopping the ammonia introduction reaction after monitoring the reaction by liquid chromatography until a chloroacetic acid peak disappears. Wherein the mol ratio of chloroacetic acid to ammonia to 4-dimethylaminopyridine is 1: 2.2: 0.03, the weight of methanol and n-propanol was 4 times the weight of chloroacetic acid.
B: and D, cooling the reaction liquid obtained by the ammonolysis reaction in the step A to 40-45 ℃, filtering, washing and drying a filter cake by using methanol to obtain a product glycine, and filtering mother liquor to perform the operation in the step C.
C: and D, cooling the filtered mother liquor obtained in the step B to-20 ℃, filtering to obtain mixed crystal solid containing ammonium chloride and glycine, and recycling the filtered filtrate to the step A.
D: c, washing the mixed crystal solid obtained in the step C with methanol, washing with water, filtering and drying to obtain an ammonium chloride product, wherein in the process, washing liquid obtained after washing with methanol is sent to the step B and is mixed with the washing liquid obtained after washing with methanol in the step B for centralized treatment; and (3) circularly washing the washing liquid after water washing, returning the washing liquid to the methanol washing step when the concentration of glycine in the washing liquid after water washing is more than 20%, rectifying the washing liquid to recover the solvent in the methanol washing process, and sending the residual aqueous solution to the water washing process again to realize zero discharge of wastewater.
Example 5:
this example presents a method for the catalytic synthesis of glycine in a homogeneous system. The method comprises the following specific steps:
a: using chloroacetic acid and ammonia gas as raw materials, carrying out ammonolysis reaction in the presence of a substituted pyridine catalyst (2-methylpyridine) and a solvent (n-butyl alcohol), adding perchloroacetic acid, 2-methylpyridine and n-butyl alcohol into a reactor with reflux condensation and stirring, stirring and mixing for 30min, controlling the temperature of a reaction system to be 60-65 ℃, introducing ammonia gas into the reactor, and stopping the ammonia introduction reaction after the chloroacetic acid peak disappears through liquid chromatography monitoring reaction. Wherein the mol ratio of chloroacetic acid to ammonia to 2-methylpyridine is 1: 2.5: 0.04, wherein the weight of the n-butyl alcohol is 6 times of that of the chloroacetic acid.
B: and D, cooling the reaction liquid obtained by the ammonolysis reaction in the step A to 40-45 ℃, filtering, washing and drying a filter cake by using methanol to obtain a product glycine, and filtering mother liquor to perform the operation in the step C.
C: and D, cooling the filtered mother liquor obtained in the step B to 10 ℃, filtering to obtain mixed crystal solid containing ammonium chloride and glycine, and recycling the filtered filtrate to the step A.
D: c, washing the mixed crystal solid obtained in the step C with methanol, washing with water, filtering and drying to obtain an ammonium chloride product, wherein in the process, washing liquid obtained after washing with methanol is sent to the step B and is mixed with the washing liquid obtained after washing with methanol in the step B for centralized treatment; and (3) circularly washing the washing liquid after water washing, returning the washing liquid to the methanol washing step when the concentration of glycine in the washing liquid after water washing is more than 20%, rectifying the washing liquid to recover the solvent in the methanol washing process, and sending the residual aqueous solution to the water washing process again to realize zero discharge of wastewater.
Example 6:
this example presents a method for the catalytic synthesis of glycine in a homogeneous system. The method comprises the following specific steps:
a: using chloroacetic acid and ammonia gas as raw materials, carrying out ammonolysis reaction in the presence of a substituted pyridine catalyst (3, 5-lutidine) and a solvent (methanol and ethanol), adding perchloroacetic acid, 3, 5-lutidine, methanol and ethanol into a reactor with reflux condensation and stirring, stirring and mixing for 20min, controlling the temperature of a reaction system to be 60-65 ℃, introducing ammonia gas into the reactor, and stopping the ammonia introduction reaction when the chloroacetic acid peak disappears through liquid chromatography monitoring reaction. Wherein the mol ratio of chloroacetic acid to ammonia to 3, 5-dimethylpyridine is 1: 2.4: 0.02, the weight of methanol and ethanol is 5 times of that of chloroacetic acid.
B: and D, cooling the reaction liquid obtained by the ammonolysis reaction in the step A to 40-45 ℃, filtering, washing a filter cake with ethanol, drying to obtain a product glycine, and filtering the mother liquor to perform the operation in the step C.
C: and D, cooling the filtered mother liquor obtained in the step B to-20-10 ℃, filtering to obtain mixed crystal solid containing ammonium chloride and glycine, and recycling the filtered filtrate to the step A.
D: c, washing the mixed crystal solid obtained in the step C with ethanol, washing with water, filtering and drying to obtain an ammonium chloride product, wherein in the process, washing liquid obtained after ethanol washing is sent to the step B and is mixed with the washing liquid obtained after ethanol washing in the step B for centralized treatment; and (3) circularly washing the washing liquid after water washing, returning the washing liquid to the ethanol washing step when the concentration of glycine in the washing liquid after water washing is more than 20%, rectifying the washing liquid to recover the solvent in the ethanol washing process, and sending the residual aqueous solution to the water washing process again to realize zero discharge of wastewater.
Example 7:
this example presents a method for the catalytic synthesis of glycine in a homogeneous system. The method comprises the following specific steps:
a: using chloroacetic acid and ammonia gas as raw materials, carrying out ammonolysis reaction in the presence of a substituted pyridine catalyst (2, 4-lutidine) and a solvent (ethanol), adding perchloroacetic acid, 2, 4-lutidine and ethanol into a reactor with reflux condensation and stirring, stirring and mixing for 15min, controlling the temperature of a reaction system to be 60-65 ℃, introducing ammonia gas into the reactor, and stopping the ammonia introduction reaction by monitoring the reaction through liquid chromatography until a chloroacetic acid peak disappears. Wherein the mol ratio of chloroacetic acid, ammonia gas and 2, 4-dimethylpyridine is 1: 2.0: 0.05, the weight of ethanol is 3 times of that of chloroacetic acid.
B: and D, cooling the reaction liquid obtained by the ammonolysis reaction in the step A to 40-45 ℃, filtering, washing a filter cake with ethanol, drying to obtain a product glycine, and filtering the mother liquor to perform the operation in the step C.
C: and D, cooling the filtered mother liquor obtained in the step B to-5 ℃, filtering to obtain mixed crystal solid containing ammonium chloride and glycine, and recycling the filtered filtrate to the step A.
D: c, washing the mixed crystal solid obtained in the step C with ethanol, washing with water, filtering and drying to obtain an ammonium chloride product, wherein in the process, washing liquid obtained after ethanol washing is sent to the step B and is mixed with the washing liquid obtained after ethanol washing in the step B for centralized treatment; and (3) circularly washing the washing liquid after water washing, returning the washing liquid to the ethanol washing step when the concentration of glycine in the washing liquid after water washing is more than 20%, rectifying the washing liquid to recover the solvent in the ethanol washing process, and sending the residual aqueous solution to the water washing process again to realize zero discharge of wastewater.
Example 8:
this example presents a method for the catalytic synthesis of glycine in a homogeneous system. The method comprises the following specific steps:
a: adding 96.5g of 98% chloroacetic acid (1.0 mol), 1.08g of 99%3, 5-lutidine (0.01 mol) and 200mL of methanol into a reaction vessel with a stirrer, a reflux condenser and a thermometer, starting the stirrer, stirring and mixing for 10min, introducing ammonia gas into the reaction vessel, immediately generating white precipitate, controlling the reaction temperature at 60-65 ℃, stopping introducing ammonia after the chloroacetic acid completely reacts by HPLC monitoring reaction, introducing about 37g of ammonia in the reaction process, and reacting for 2 h.
B: and C, cooling the reaction liquid obtained by the ammonolysis reaction in the step A to 40-45 ℃, filtering, washing a filter cake with a small amount of methanol, and drying to obtain 68.4g of glycine product with the content of 98.2%.
C: and D, freezing and cooling the filtered mother liquor obtained in the step B to-0 ℃, filtering to obtain mixed crystal solid containing ammonium chloride and glycine, and recycling the filtered filtrate to the step A as a solvent to participate in the reaction.
D: c, washing the mixed crystal solid obtained in the step C with methanol or ethanol, washing with water, filtering and drying to obtain 32.1g of 98.0% ammonium chloride, wherein in the process, the washing liquid obtained after washing with methanol or ethanol is sent to the step B and is mixed with the washing liquid obtained after washing with methanol in the step B for centralized treatment; and (3) circularly washing the washing liquid after water washing, returning the washing liquid to the methanol washing step when the concentration of glycine in the washing liquid after water washing is more than 20%, rectifying the washing liquid to recover the solvent in the methanol washing process, and sending the residual aqueous solution to the water washing process again to realize zero discharge of wastewater.
Example 9:
this example presents a method for the catalytic synthesis of glycine in a homogeneous system. The method comprises the following specific steps:
a: adding 96.5g of 98% chloroacetic acid (1.0 mol), 3.24g of 99%2, 4-lutidine (0.03 mol) and 200mL of ethanol into a reaction vessel with a stirrer, a reflux condenser and a thermometer, starting the stirrer, stirring and mixing for 10min, introducing ammonia gas into the reaction vessel, immediately generating white precipitate, controlling the reaction temperature at 60-65 ℃, stopping introducing ammonia after the chloroacetic acid completely reacts by HPLC monitoring reaction, introducing about 40g of ammonia in the reaction process, and reacting for 2 h.
B: and C, cooling the reaction liquid obtained by the ammonolysis reaction in the step A to 40-45 ℃, filtering, washing a filter cake with a small amount of methanol, and drying to obtain 66.2g of glycine product with the content of 98.5%.
C: and D, freezing and cooling the filtered mother liquor obtained in the step B to-10 ℃, filtering to obtain mixed crystal solid containing ammonium chloride and glycine, and recycling the filtered filtrate to the step A as a solvent to participate in the reaction.
D: c, washing the mixed crystal solid obtained in the step C with methanol or ethanol, washing with water, filtering and drying to obtain 34.7g of 98.2% ammonium chloride, wherein in the process, the washing liquid obtained after washing with methanol or ethanol is sent to the step B and is mixed with the washing liquid obtained after washing with methanol in the step B for centralized treatment; and (3) circularly washing the washing liquid after water washing, returning the washing liquid to the methanol washing step when the concentration of glycine in the washing liquid after water washing is more than 20%, rectifying the washing liquid to recover the solvent in the methanol washing process, and sending the residual aqueous solution to the water washing process again to realize zero discharge of wastewater.
Example 10:
this example presents a method for the catalytic synthesis of glycine in a homogeneous system. The method comprises the following specific steps:
a: adding 96.5g of 98% chloroacetic acid (1.0 mol), 4.70g of 99% 2-methylpyridine (0.05 mol), 160mL of ethylene glycol and 40mL of propanol into a reaction vessel with a stirrer, a reflux condenser and a thermometer, starting the stirrer, stirring and mixing for 10min, introducing ammonia gas into the reaction vessel, immediately generating a white precipitate, controlling the reaction temperature at 60-65 ℃, stopping introducing ammonia after the reaction of chloroacetic acid is completely monitored by HPLC (high performance liquid chromatography), introducing about 41g of ammonia in the reaction process, and reacting for 2 h.
B: and C, cooling the reaction liquid obtained by the ammonolysis reaction in the step A to 40-45 ℃, filtering, washing a filter cake with a small amount of methanol, and drying to obtain 67.3g of glycine product with the content of 98.9%.
C: and D, freezing and cooling the filtered mother liquor obtained in the step B to-0 ℃, filtering to obtain mixed crystal solid containing ammonium chloride and glycine, and recycling the filtered filtrate to the step A as a solvent to participate in the reaction.
D: c, washing the mixed crystal solid obtained in the step C with methanol or ethanol, washing with water, filtering and drying to obtain 30.4g of 98.5% ammonium chloride, wherein in the process, the washing liquid obtained after washing with methanol or ethanol is sent to the step B and is mixed with the washing liquid obtained after washing with methanol in the step B for centralized treatment; and (3) circularly washing the washing liquid after water washing, returning the washing liquid to the methanol washing step when the concentration of glycine in the washing liquid after water washing is more than 20%, rectifying the washing liquid to recover the solvent in the methanol washing process, and sending the residual aqueous solution to the water washing process again to realize zero discharge of wastewater.
Example 11:
this example presents a method for the catalytic synthesis of glycine in a homogeneous system. The method comprises the following specific steps:
a: adding 1.45Kg of 98% chloroacetic acid (15 mol), 32.4g of 99%3, 5-lutidine (0.3 mol) and 2.5L of ethanol into a reaction vessel with a stirrer, a reflux condenser and a thermometer, starting the stirrer, stirring and mixing for 10min, introducing ammonia gas into the reaction vessel, immediately generating white precipitate, controlling the reaction temperature at 60-65 ℃, stopping introducing ammonia after the chloroacetic acid completely reacts by HPLC monitoring reaction, introducing about 610g of ammonia in the reaction process, and reacting for 2 h.
B: and C, cooling the reaction liquid obtained by the ammonolysis reaction in the step A to 40-45 ℃, filtering, washing a filter cake with a small amount of methanol, and drying to obtain 1.01kg of glycine product with the content of 98.6%.
C: and D, freezing and cooling the filtered mother liquor obtained in the step B to-0 ℃, filtering to obtain mixed crystal solid containing ammonium chloride and glycine, and recycling the filtered filtrate to the step A as a solvent to participate in the reaction.
D: washing the mixed crystal solid obtained in the step C with methanol or ethanol, washing with water, filtering and drying to obtain 521g of 98.0% ammonium chloride, wherein in the process, washing liquid obtained after washing with methanol or ethanol is sent to the step B and is mixed with the washing liquid obtained after washing with methanol in the step B for centralized treatment; and (3) circularly washing the washing liquid after water washing, returning the washing liquid to the methanol washing step when the concentration of glycine in the washing liquid after water washing is more than 20%, rectifying the washing liquid to recover the solvent in the methanol washing process, and sending the residual aqueous solution to the water washing process again to realize zero discharge of wastewater.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (6)
1. A method for catalytically synthesizing glycine in a homogeneous system is characterized by comprising the following steps: the method comprises the following steps:
a: taking chloroacetic acid and ammonia gas as raw materials, and carrying out ammonolysis reaction in the presence of a substituted pyridine catalyst and a solvent;
b: filtering the reaction liquid obtained by the ammonolysis reaction in the step A, washing a filter cake to obtain a product glycine, and filtering mother liquor to perform the operation in the step C;
c: cooling and filtering the filtered mother liquor obtained in the step B to obtain mixed crystal solid containing ammonium chloride and glycine, and recycling the filtered filtrate to the step A;
d: c, washing, filtering and drying the mixed crystal solid obtained in the step C to obtain an ammonium chloride product,
in the step A, the mol ratio of chloroacetic acid, ammonia gas and substituted pyridine catalyst is 1: 2.0-2.5: 0.01 to 0.05, the weight of the solvent is 2 to 8 times of that of chloroacetic acid,
the substituted pyridine catalyst is selected from one of 3, 5-lutidine, 2, 4-lutidine, 4-methylpyridine, 2-methylpyridine and 4-dimethylaminopyridine, and the solvent is selected from one or more of methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, ethylene glycol, propylene glycol and butanediol.
2. The method for the catalytic synthesis of glycine in a homogeneous system according to claim 1, wherein: and in the step A, adding perchloroacetic acid, a substituted pyridine catalyst and a solvent into a reactor with reflux condensation and stirring, stirring and mixing for 10-30 min, controlling the temperature of a reaction system to be 60-65 ℃, introducing ammonia gas into the reactor, and stopping the ammonia introduction reaction after the chloroacetic acid peak disappears through liquid chromatography monitoring reaction.
3. The method for the catalytic synthesis of glycine in a homogeneous system according to claim 1, wherein: and in the step B, cooling the reaction liquid obtained by the ammonolysis reaction in the step A to 40-45 ℃, filtering, washing a filter cake by methanol or ethanol, and drying to obtain a product glycine.
4. The method for the catalytic synthesis of glycine in a homogeneous system according to claim 1, wherein: in the step C, the temperature of the cooled filtrate is-20-10 ℃.
5. The method of claim 4, wherein the method comprises the steps of: in the step D, washing the mixed crystal solid obtained in the step C with methanol or ethanol, washing with water, filtering and drying to obtain an ammonium chloride product, sending a washing liquid obtained after washing with methanol or ethanol to the step B, and mixing the washing liquid with the washing liquid obtained after washing with methanol or ethanol in the step B for centralized treatment; and (3) recycling the washing liquid after water washing for water washing, and returning the washing liquid to the methanol or ethanol washing step when the concentration of glycine in the washing liquid after water washing is more than 20%.
6. The method of claim 5, wherein the method comprises the steps of: in the methanol or ethanol washing process, after the solvent is recovered by rectifying the washing liquid, the residual water solution is sent to the water washing process.
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