CN111100021A - Synthesis method of glycine - Google Patents
Synthesis method of glycine Download PDFInfo
- Publication number
- CN111100021A CN111100021A CN201911407662.XA CN201911407662A CN111100021A CN 111100021 A CN111100021 A CN 111100021A CN 201911407662 A CN201911407662 A CN 201911407662A CN 111100021 A CN111100021 A CN 111100021A
- Authority
- CN
- China
- Prior art keywords
- alcohol
- mother liquor
- impurities
- reaction
- glycine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
- C07C227/42—Crystallisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of glycine, which comprises the following steps: adding the mother solution, the silicone oil and the crystallization promoter into a reaction kettle, and heating to 75-85 ℃; wherein the mother liquor contains an alcohol-water system and urotropine; dropwise adding chloroacetic acid solution into the reaction kettle, introducing ammonia gas into the reaction kettle at the same time, ensuring the pH value to be 6.5-8, and keeping the temperature for 20-40 minutes in the reaction process; after the reaction is finished, centrifugally separating out mixed crystals containing glycine, and remaining mother liquor containing impurities and a byproduct ammonium dichloroacetate; separating glycine from the mixed crystal, sending the mother liquor containing impurities and a byproduct ammonium dichloroacetate into a degumming kettle, changing the magnetic field of the mother liquor, and removing the byproduct ammonium dichloroacetate and the impurities by an alcohol precipitation method to obtain the mother liquor. The method effectively controls the crystal form granularity and the wall scraping phenomenon, simultaneously controls the content of the solvent in the mixed crystal, effectively separates urotropine and impurities in the synthesis process, and avoids bringing the urotropine and the impurities into the mixed crystal separation process.
Description
Technical Field
The invention relates to a synthesis method of glycine.
Background
Currently, glycine is the amino acid with the simplest structure and the smallest molecular weight, is widely used in the fields of medicines, foods, feeds and chemical industry, and is a main raw material for producing herbicide glyphosate. The synthesis method mainly comprises a Scherk method, a Bucherer method, a phase transfer catalysis method and a chloroacetic acid ammonolysis method, and the chloroacetic acid ammonolysis method is mainly used in China.
70% of the domestic glycine capacity is used for producing glyphosate, and the quality of the glycine directly determines the quality of the glyphosate. The purity of the glycine is required to be more than or equal to 98.5 percent and the cl-content is required to be less than or equal to 0.4 percent in the general production of the glyphosate, but the current domestic process for producing the glycine has the following disadvantages:
1. the amount of the mother liquor is large. At present, 3 tons of mother liquor can be generated when 1 ton of glycine is produced, the energy consumption is high, and the pollution is serious;
2. and degrading urotropin. In the domestic production process, the urotropine is mixed in the ammonium chloride, the temperature of the ammonium chloride during distillation and concentration is 180 ℃, the urotropine is degraded and yellowed, formaldehyde is generated after the urotropine is degraded, the urotropine has a sterilization effect, the quality of the ammonium chloride is seriously influenced, and in addition, the urotropine cannot be recycled, so that the resource waste is caused;
3. the yield is low. The yield of the domestic original chloroacetic acid ammonolysis process is only about 85 percent, partial recycling of the urotropine can be realized only by using solid chloroacetic acid and adopting methanol-ethanol and other alcohol-water systems through an improved method, the yield can be more than 95 percent, but the process is not suitable for liquid chloroacetic acid; the purity of the liquid chloroacetic acid is about 95%, and other impurities mainly comprise dichloroacetic acid, a small amount of trichloroacetic acid and acetic acid, so that a large amount of impurities are generated in the reaction process, and the mother liquor is difficult to reuse for many times.
The main and side reaction equations are as follows:
the process is a precipitation method, namely glycine and ammonium chloride are directly precipitated in a crystal form in the synthesis process by using the difference of solubility. However, the crystal which appears rapidly releases crystallization heat, and is easy to form peritectic and wall scraping phenomena, so that the PH value in the reaction liquid is unequal, and further, the urotropine is degraded along with the change of the PH value (particularly when the PH value is less than or equal to 6), thereby influencing the yield of the reaction and the generation of a large amount of impurities, and causing difficulty to the mixed crystal separation process.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a synthesis method of glycine, which effectively controls the crystal form granularity and the wall scraping phenomenon, simultaneously controls the solvent content in mixed crystals, effectively separates urotropine and impurities (byproducts generated by the reaction of dichloroacetic acid and trichloroacetic acid) in a synthesis process, and avoids bringing the urotropine into a mixed crystal separation process, such as the mixed crystal separation process, and still returns to the synthesis process along with final mother liquor.
In order to solve the technical problems, the technical scheme of the invention is as follows: a method for synthesizing glycine comprises the following steps:
adding the mother solution, the silicone oil and the crystallization promoter into a reaction kettle, and heating to 75-85 ℃; wherein the mother liquor contains an alcohol-water system and urotropine;
dropwise adding chloroacetic acid solution into the reaction kettle, introducing ammonia gas into the reaction kettle at the same time, ensuring the pH value to be 6.5-8, and keeping the temperature for 20-40 minutes in the reaction process;
after the reaction is finished, centrifugally separating out mixed crystals containing glycine, and remaining mother liquor containing impurities and a byproduct ammonium dichloroacetate;
separating glycine from the mixed crystal, sending the mother liquor containing impurities and a byproduct ammonium dichloroacetate into a degumming kettle, changing the magnetic field of the mother liquor, and removing the byproduct ammonium dichloroacetate and the impurities by an alcohol precipitation method to obtain the mother liquor.
Further, the alcohol-water system contains alcohol and water, and the mass ratio of the alcohol to the water is (180-250): (5-40).
Further, the alcohol is at least one of methanol and ethanol.
Further, the alcohol-water system contains alcohol and water, and in a reaction kettle,
alcohol: 180-250 parts by weight;
water: 5-40 parts by weight;
chloroacetic acid: 90-100 parts by weight;
urotropin: 10 to 14 parts by weight;
the mol ratio of chloroacetic acid to ammonia gas is 1: (2.0-2.5);
the silicone oil is one ten thousandth to five ten thousandth of the mass of the alcohol-water system;
the crystallization promoter is one ten thousandth to five ten thousandth of the mass of the alcohol-water system.
Further, the mixed crystal also contains ammonium chloride.
Further, the method comprises the following steps:
and adding the mother liquor with impurities and a byproduct ammonium dichloroacetate removed into the reaction kettle again for reaction.
Further, the magnetic ball with specific gravity greater than 1 is used to change the magnetic field of the mother liquid.
Further, the solvent in the chloroacetic acid solution is an aqueous solution of at least one of methanol and ethanol.
Further, the dripping speed of dripping the chloroacetic acid solution is 3 to 10 percent of the total chloroacetic acid per minute.
After the technical scheme is adopted, the invention has the following beneficial effects:
1. the method utilizes the dissolubility of substances, alcohol is used for separating out mixed crystals (namely glycine and ammonium chloride), urotropine is retained in the reacted mother liquor, the reacted mother liquor adopts a magnetic ball in the process of returning to a reaction kettle, ammonium dichloroacetate and impurities are attached to the surface of a filler with the specific gravity of more than 1, so that the separation purpose is achieved, meanwhile, the ammonium dichloroacetate is taken as an adsorbate of a urotropine degradation product to take away the impurities, so that the color and the viscosity of the reacted mother liquor are ensured, the byproducts and the impurities do not enter the separation working procedures of the glycine and the ammonium chloride, if the separation working procedures are entered, the final and separated mother liquor is returned to the reaction kettle, the byproducts are continuously attached by a magnetic field, and the separation method realizes that no mother liquor is generated in the whole production process;
2. according to the invention, by adding the silicone oil and the crystallization assistant, the adhesion of by-products and impurities on the surface of the magnetic ball is accelerated;
3. the dripping amount of the chloroacetic acid solution is reasonably controlled, the reaction speed is improved, the reaction time and temperature of the side reaction are controlled, and the smooth proceeding of the main reaction is ensured to the maximum extent.
Detailed Description
The invention provides a synthesis method of glycine, and a person skilled in the art can use the contents to reference the text and appropriately improve the process parameters to realize the synthesis. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
A method for synthesizing glycine comprises the following steps:
adding the mother solution, the silicone oil and the crystallization promoter into a reaction kettle, and heating to 75-85 ℃; wherein the mother liquor contains an alcohol-water system and urotropine;
dropwise adding chloroacetic acid solution into the reaction kettle, introducing ammonia gas into the reaction kettle at the same time, ensuring the pH value to be 6.5-8, and keeping the temperature for 20-40 minutes in the reaction process;
after the reaction is finished, centrifugally separating out mixed crystals containing glycine, and remaining mother liquor containing impurities and a byproduct ammonium dichloroacetate;
separating glycine from the mixed crystal, sending the mother liquor containing impurities and a byproduct ammonium dichloroacetate into a degumming kettle, changing the magnetic field of the mother liquor, and removing the byproduct ammonium dichloroacetate and the impurities by an alcohol precipitation method to obtain the mother liquor.
Specifically, the alcohol is at least one of methanol and ethanol.
Specifically, the alcohol-water system contains alcohol and water, and in a reaction kettle,
alcohol: 180-250 parts by weight;
water: 5-40 parts by weight;
chloroacetic acid: 90-100 parts by weight;
urotropin: 10 to 14 parts by weight;
the mol ratio of chloroacetic acid to ammonia gas is 1: (2.0-2.5);
the silicone oil is one ten thousandth to five ten thousandth of the mass of the alcohol-water system;
the crystallization promoter is one ten thousandth to five ten thousandth of the mass of the alcohol-water system.
Specifically, the mixed crystal also contains ammonium chloride.
Specifically, the method further comprises the following steps:
and adding the mother liquor with impurities and a byproduct ammonium dichloroacetate removed into the reaction kettle again for reaction, and supplementing urotropine to the corresponding weight part.
Specifically, the magnetic ball with specific gravity greater than 1 is used to change the magnetic field of the mother liquid.
In the invention, the addition of the silicone oil and the crystallization promoter accelerates the adhesion of by-products and impurities on the surface of the magnetic ball.
Specifically, the solvent in the chloroacetic acid solution is an aqueous solution of at least one of methanol and ethanol.
Specifically, the dripping speed of dripping the chloroacetic acid solution is 3 to 10 percent of the total chloroacetic acid per minute. In the invention, the dripping amount of the chloroacetic acid solution is reasonably controlled, the reaction speed is improved, the reaction time and temperature of the side reaction are controlled, and the smooth proceeding of the main reaction is ensured to the maximum extent.
The method utilizes the dissolubility of substances, alcohol is used for separating out mixed crystals (namely glycine and ammonium chloride), urotropine is left in the reacted mother liquor, the ammonium dichloroacetate and impurities are attached to the surface of a filler with the specific gravity being more than 1 by adopting a magnetic ball in the process of returning the reacted mother liquor to a reaction kettle, so that the separation purpose is achieved, meanwhile, the ammonium dichloroacetate is taken as an adsorbate of a urotropine degradation product to take away the impurities, so that the color and the viscosity of the reacted mother liquor are ensured, the byproducts and the impurities do not enter the separation working procedures of the glycine and the ammonium chloride, if the separation working procedures are carried out, the final and separated mother liquor is returned to the reaction kettle, the byproducts are attached by a magnetic field continuously, and no mother liquor is generated in the whole production process by using a secondary separation method;
in order that the present invention may be more clearly understood, the following detailed description of the present invention is given with reference to specific examples.
Example one
A method for synthesizing glycine comprises the following steps:
adding the mother solution, the silicone oil and the crystallization promoter into a reaction kettle, and heating to about 78 ℃; wherein the mother liquor contains an alcohol-water system and urotropine;
dropwise adding chloroacetic acid solution into the reaction kettle, introducing ammonia gas into the reaction kettle at the same time, ensuring the pH value to be about 7, and keeping the temperature for 30 minutes in the reaction process;
after the reaction is finished, centrifugally separating out mixed crystals containing glycine, and remaining mother liquor containing impurities and a byproduct ammonium dichloroacetate;
separating glycine from the mixed crystal, sending the mother liquor containing impurities and a byproduct ammonium dichloroacetate into a degumming kettle, changing the magnetic field of the mother liquor, and removing the byproduct ammonium dichloroacetate and the impurities by an alcohol precipitation method to obtain the mother liquor.
The alcohol-water system contains alcohol and water, in a reaction kettle,
alcohol: 180 parts by weight;
water: 5 parts by weight;
chloroacetic acid: 90 parts by weight;
urotropin: 10 parts by weight;
the mol ratio of chloroacetic acid to ammonia gas is 1: 2.0;
the silicone oil is one ten thousandth of the mass of the alcohol-water system;
the crystallization aid is one ten-thousandth of the mass of an alcohol-water system.
The mixed crystals also contain ammonium chloride.
The alcohol is methanol.
The method also comprises the following steps:
and adding the mother liquor with impurities and a byproduct ammonium dichloroacetate removed into the reaction kettle again for reaction, and supplementing urotropine to the corresponding weight part.
The magnetic ball with specific gravity greater than 1 is used to change the magnetic field of mother liquid.
The solvent in the chloroacetic acid solution is ethanol.
The dropping speed of the chloroacetic acid solution is 5% of the total chloroacetic acid amount per minute.
Example two
A method for separating glycine comprises the following steps:
adding the mother solution, the silicone oil and the crystallization promoter into a reaction kettle, and heating to 85 ℃; wherein the mother liquor contains an alcohol-water system and urotropine;
dropwise adding chloroacetic acid solution into the reaction kettle, introducing ammonia gas into the reaction kettle at the same time to ensure that the pH value is 8, and keeping the temperature for 40 minutes in the reaction process;
after the reaction is finished, centrifugally separating out mixed crystals containing glycine, and remaining mother liquor containing impurities and a byproduct, namely diaminoacetic acid;
separating glycine from the mixed crystal, sending the mother liquor containing impurities and the byproduct diaminoacetic acid into a degumming kettle, changing the magnetic field of the mother liquor, and removing the byproduct diaminoacetic acid and the impurities by an alcohol precipitation method to obtain the mother liquor.
The alcohol-water system contains alcohol and water, in a reaction kettle,
alcohol: 250 parts by weight;
water: 40 parts by weight;
chloroacetic acid: 100 parts by weight;
urotropin: 14 parts by weight;
the mol ratio of chloroacetic acid to ammonia gas is 1: 2.5;
the silicone oil is five ten-thousandth of the mass of the alcohol-water system;
the crystallization promoter is five ten-thousandths of the mass of the alcohol-water system.
The mixed crystals also contain ammonium chloride.
The alcohol is ethanol.
The method also comprises the following steps:
and adding the mother liquor with impurities and a byproduct ammonium dichloroacetate removed into the reaction kettle again for reaction, and supplementing urotropine to the corresponding weight part.
The magnetic ball with specific gravity greater than 1 is used to change the magnetic field of mother liquid.
The solvent in the chloroacetic acid solution is ethanol.
The dropping speed of the chloroacetic acid solution is 10 percent of the total chloroacetic acid per minute.
EXAMPLE III
A method for separating glycine comprises the following steps:
adding the mother solution, the silicone oil and the crystallization promoter into a reaction kettle, and heating to 75 ℃; wherein the mother liquor contains an alcohol-water system and urotropine;
dropwise adding chloroacetic acid solution into the reaction kettle, introducing ammonia gas into the reaction kettle at the same time, ensuring the pH value to be 6.5, and keeping the temperature for 20 minutes in the reaction process;
after the reaction is finished, centrifugally separating out mixed crystals containing glycine, and remaining mother liquor containing impurities and a byproduct ammonium dichloroacetate;
separating glycine from the mixed crystal, sending the mother liquor containing impurities and a byproduct ammonium dichloroacetate into a degumming kettle, changing the magnetic field of the mother liquor, and removing the byproduct ammonium dichloroacetate and the impurities by an alcohol precipitation method to obtain the mother liquor.
The alcohol-water system contains alcohol and water, in a reaction kettle,
alcohol: 220 parts by weight;
water: 20 parts by weight;
chloroacetic acid: 95 parts by weight;
urotropin: 12 parts by weight;
the mol ratio of chloroacetic acid to ammonia gas is 1: 2.2;
the silicone oil is three-ten-thousandth of the mass of the alcohol-water system;
the crystallization promoter is three-ten-thousandth of the mass of the alcohol-water system.
The mixed crystals also contain ammonium chloride.
The method also comprises the following steps:
and adding the mother liquor with impurities and a byproduct ammonium dichloroacetate removed into the reaction kettle again for reaction, and supplementing urotropine to the corresponding weight part.
The magnetic ball with specific gravity greater than 1 is used to change the magnetic field of mother liquid.
The solvent in the chloroacetic acid solution is ethanol.
The dropping speed of the chloroacetic acid solution is 7% of the total chloroacetic acid per minute.
The alcohol is ethanol.
In the three embodiments, the impurities and the byproduct ammonium dichloroacetate are separated from the mother liquor through the magnetic ball, and the mother liquor for separating the impurities and the byproduct returns to the reaction kettle for reaction, so that no mother liquor is generated in the whole production process, and urotropine and impurities are not generated in the separation process of the mixed crystal, thereby being beneficial to the separation of components in the mixed crystal.
The above embodiments are described in further detail to solve the technical problems, technical solutions and advantages of the present invention, and it should be understood that the above embodiments are only examples of the present invention and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method for synthesizing glycine is characterized by comprising the following steps:
adding the mother solution, the silicone oil and the crystallization promoter into a reaction kettle, and heating to 75-85 ℃; wherein the mother liquor contains an alcohol-water system and urotropine;
dropwise adding chloroacetic acid solution into the reaction kettle, introducing ammonia gas into the reaction kettle at the same time, ensuring the pH value to be 6.5-8, and keeping the temperature for 20-40 minutes in the reaction process;
after the reaction is finished, centrifugally separating out mixed crystals containing glycine, and remaining mother liquor containing impurities and a byproduct ammonium dichloroacetate;
separating glycine from the mixed crystal, sending the mother liquor containing impurities and a byproduct ammonium dichloroacetate into a degumming kettle, changing the magnetic field of the mother liquor, and removing the byproduct ammonium dichloroacetate and the impurities by an alcohol precipitation method to obtain the mother liquor.
2. The method of synthesis according to claim 1,
the alcohol-water system contains alcohol and water, and the mass ratio of the alcohol to the water is (180-250): (5-40).
3. The method of synthesis according to claim 2,
the alcohol is at least one of methanol and ethanol.
4. The method of synthesis according to claim 1,
the alcohol-water system contains alcohol and water, in a reaction kettle,
alcohol: 180-250 parts by weight;
water: 5-40 parts by weight;
chloroacetic acid: 90-100 parts by weight;
urotropin: 10 to 14 parts by weight;
the mol ratio of chloroacetic acid to ammonia gas is 1: (2.0-2.5);
the silicone oil is one ten thousandth to five ten thousandth of the mass of the alcohol-water system;
the crystallization promoter is one ten thousandth to five ten thousandth of the mass of the alcohol-water system.
5. The method of synthesis according to claim 1,
the mixed crystals also contain ammonium chloride.
6. The method of claim 1, further comprising the steps of:
and adding the mother liquor with impurities and a byproduct ammonium dichloroacetate removed into the reaction kettle again for reaction.
7. The method of synthesis according to claim 1,
the magnetic ball with specific gravity greater than 1 is used to change the magnetic field of mother liquid.
8. The method of synthesis according to claim 1,
the solvent in the chloroacetic acid solution is an aqueous solution of at least one of methanol and ethanol.
9. The method of synthesis according to claim 4,
the dropping speed of the chloroacetic acid solution is 3-10% of the total chloroacetic acid per minute.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911407662.XA CN111100021A (en) | 2019-12-31 | 2019-12-31 | Synthesis method of glycine |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911407662.XA CN111100021A (en) | 2019-12-31 | 2019-12-31 | Synthesis method of glycine |
Publications (1)
Publication Number | Publication Date |
---|---|
CN111100021A true CN111100021A (en) | 2020-05-05 |
Family
ID=70423900
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201911407662.XA Pending CN111100021A (en) | 2019-12-31 | 2019-12-31 | Synthesis method of glycine |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111100021A (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1340498A (en) * | 2000-08-31 | 2002-03-20 | 浙江新安化工集团股份有限公司 | Process for preparing glycine |
CN103086904A (en) * | 2011-11-04 | 2013-05-08 | 海南正业中农高科股份有限公司 | Method of production of glycine by circulation environmental-friendly method in reactor |
CN103086903A (en) * | 2011-11-04 | 2013-05-08 | 海南正业中农高科股份有限公司 | Preparation method of mixed crystal of glycine and ammonium chloride |
CN105859571A (en) * | 2015-01-19 | 2016-08-17 | 刘长飞 | Method for producing glycine by mixed solvent method |
CN109574864A (en) * | 2018-12-10 | 2019-04-05 | 四川省乐山市福华通达农药科技有限公司 | A kind of glycine new technique for synthesizing |
-
2019
- 2019-12-31 CN CN201911407662.XA patent/CN111100021A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1340498A (en) * | 2000-08-31 | 2002-03-20 | 浙江新安化工集团股份有限公司 | Process for preparing glycine |
CN103086904A (en) * | 2011-11-04 | 2013-05-08 | 海南正业中农高科股份有限公司 | Method of production of glycine by circulation environmental-friendly method in reactor |
CN103086903A (en) * | 2011-11-04 | 2013-05-08 | 海南正业中农高科股份有限公司 | Preparation method of mixed crystal of glycine and ammonium chloride |
CN105859571A (en) * | 2015-01-19 | 2016-08-17 | 刘长飞 | Method for producing glycine by mixed solvent method |
CN109574864A (en) * | 2018-12-10 | 2019-04-05 | 四川省乐山市福华通达农药科技有限公司 | A kind of glycine new technique for synthesizing |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103476938B (en) | METHIONINE and the production method of associated products | |
CN104473120B (en) | A kind of production technology of monosodium glutamate | |
CN105600763B (en) | A kind of method that fluoride salt method of purification produces industrial monoammonium phosphate | |
CN101602701A (en) | Produce the method for methionine(Met) | |
CN105492618A (en) | Process for the preparation of 2,5-furandicarboxylic acid | |
CN107573248A (en) | The recovery method of resolving agent R phenyl ethylamines in prepared by R-DHLA | |
CA3069786C (en) | Method for recovering phosphoric acid from fermentation broth or fermentation waste liquid and reusing the same | |
CN103167872B (en) | For the production of the method for VBT tartrate | |
CN101857212B (en) | Method for preparing food-grade monoammonium phosphate from wet-process phosphoric acid | |
CN1736870A (en) | Method for preparing potassium nitrate using nitric acid conversion methdo | |
CN111100021A (en) | Synthesis method of glycine | |
KR20100122773A (en) | Process for separating and purifying succinic acid from fermentation broth | |
CN100562493C (en) | Hot method is handled alkali-making mother solution, is produced the ammonium chloride industrialization technology | |
RU2573935C2 (en) | Method of separation and purification of 1,4-diaminobutane from fermentation solution | |
CN110922417B (en) | Method for recovering cefalexin crystallization mother liquor | |
EP3133056A1 (en) | Production method of fatty acid chloride and fatty acid chloride | |
CN112408451A (en) | Device and process for producing low-salt calcium chloride through alkaline process calcium | |
US9227916B2 (en) | Process for producing amino acid | |
CN112939032A (en) | Method for preparing potassium nitrate by nitric acid method | |
CN103420882B (en) | A kind of preparation method of L-Methionine | |
CN113214145A (en) | Production method of vitamin B6 | |
CN205933241U (en) | Utilize synthetic potassium dihydrogen phosphate's of extraction tail washings device | |
CN102874849A (en) | Method for producing anhydrous lithium chloride special for electrolyzing by using lithium recovered from lithium-containing pharmaceutical waste water | |
CN102336685B (en) | Method for preparing cyanoacetic acid through continuous dehydration | |
CN102249889B (en) | Method for extracting succinic acid from citric acid mother solution |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200505 |
|
RJ01 | Rejection of invention patent application after publication |