CN108191685B - Method for preparing glycine by catalytic oxidation of ethanolamine by ionic liquid - Google Patents

Method for preparing glycine by catalytic oxidation of ethanolamine by ionic liquid Download PDF

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CN108191685B
CN108191685B CN201711311125.6A CN201711311125A CN108191685B CN 108191685 B CN108191685 B CN 108191685B CN 201711311125 A CN201711311125 A CN 201711311125A CN 108191685 B CN108191685 B CN 108191685B
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ionic liquid
monoethanolamine
glycine
acid
glycinate
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CN108191685A (en
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王慧
张锁江
孟祥展
王耀锋
盛贵阳
刘龙
李增喜
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Institute of Process Engineering of CAS
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    • 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
    • C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a method for preparing glycine by an oxidation method, in particular to a method for preparing glycine by taking monoethanolamine solution and oxygen as reaction raw materials, reacting under the action of an ionic liquid catalyst and alkali to generate glycinate, and further acidifying the glycinate to obtain the glycine. The method has the characteristics of high conversion rate of raw materials, few byproducts, high yield, simple and convenient operation, recyclable catalyst and the like.

Description

Method for preparing glycine by catalytic oxidation of ethanolamine by ionic liquid
Technical Field
The invention relates to a method for synthesizing glycine by catalytic oxidation of monoethanolamine through ionic liquid, belonging to the technical field of catalysis.
Technical Field
Glycine is an important fine chemical intermediate, and is widely applied to the fields of pesticides, medicines, foods, feeds and the like, in the aspect of pesticides, glycine can be used for producing a novel pesticide herbicide glyphosate and a plant growth regulator glyphosate, in the aspect of medicines, glycine can be used for formulas of various amino acid infusion solutions, aureomycin buffers, L-DoPa (L-DoPa), intermediates of some important amino acids and the like, in the aspect of foods, can be used as food additives, beverage debitterizing agents, food antioxidants, preservatives and the like, in addition, glycine is widely applied to feed additives, organic solvents and daily chemical products, and is a very important fine chemical product.
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 chloroacetic acid ammoniation process takes chloroacetic acid and ammonia water as raw materials, and is prepared under the action of the urotropine catalyst, a large amount of inorganic salt is generated in the reaction process, so that the purification process of the product is complex and the loss is serious, and the urotropine catalyst is easy to decompose and difficult to recycle in the reaction process. The Strecker process mixes formaldehyde aqueous solution, sodium cyanide and ammonium chloride and then reacts at low temperature, acetic acid is added after the reaction is finished to separate out the iminoacetonitrile, then the iminoacetonitrile is dissolved in ethanol, sulfuric acid is added to be converted into aminoacetonitrile sulfate, and finally stoichiometric barium hydroxide is added to generate barium sulfate and glycine. The process takes virulent sodium cyanide as a raw material, and has the defects of serious environmental pollution, high production cost, poor product quality and the like. The development of Hydantion technology is derived from finding a substitute of hydrocyanic acid to eliminate the geographical limitation of glycine production, and the prior art is not mature. The process for preparing glycine by a biological method is still in the technical development stage at present and has no industrial report.
In recent years, there is a sequential literature reporting of a method for preparing glycine by an oxidation method: U.S. patent 4,782,183 discloses a process for the preparation of glycine using the reaction of an amino alcohol and an alkali metal hydroxide in the presence of a raney copper catalyst; patent WO 92/06069 discloses a process for the preparation of glycine, iminodiacetic acid and nitrilotriacetic acid salts, in particular by reacting monoethanolamine, diethanolamine or triethanolamine with an alkali metal hydroxide in the presence of a raney copper catalyst, wherein the catalyst can be partially regenerated by treatment with formic acid under reflux conditions; chinese patent 4,810,426 discloses a process for the preparation of N-phosphonomethylglycine by oxidation of N-phosphonomethylethanolamine or its cyclic lactone with an excess of aqueous base and a copper catalyst followed by acid neutralization of the resulting salt to produce N-phosphonomethylglycine. Although the copper catalyst or Raney copper catalyst used can convert aminoethanol into amino acid, its catalytic activity is greatly reduced during the recycling of the catalyst, resulting in a drastic increase in the cost of the process.
According to the invention, monoethanolamine solution and oxygen are used as reaction raw materials, and are reacted under the action of an ionic liquid catalyst and alkali to generate glycinate, and the glycinate is obtained by further carrying out an acidification process on the glycinate. The method has the advantages of high conversion rate, few byproducts, high yield, low catalyst consumption, difficult inactivation and the like.
Disclosure of Invention
The invention aims to develop a high-efficiency green recyclable catalyst capable of catalyzing and oxidizing monoethanolamine to synthesize glycine. In particular to a method for synthesizing glycine by catalyzing and oxidizing monoethanolamine with ionic liquid, wherein the cation of the ionic liquid can be polyalkyl-substituted imidazole, pyrrole, pyridine, piperidine, quaternary ammonium or quaternary phosphonium cation, wherein the length of an alkyl side chain is between 1 and 16, and the length of each substituent can be the same or different; the anion of the ionic liquid catalyst is [ AuCl ]4]-、[FeCl4]-、[CoCl4]2-、[MoCl6]3-、[WCl6]-、[ZnCl4]2-、[AuClBr3]-、[FeClBr3]-、[CoClBr2]-、[ZnClBr2]-、[CuCl2]-、[CuBr2]-、[W2O11]2-、[HPW12O40]2-At least one of (1).
In the process of preparing glycine by oxidizing monoethanolamine, the dosage of the ionic liquid is 0.1-50% of the molar weight of aminoethanol; the base includes NaOH, KOH, CsOH, Ba (OH)2The method comprises the steps of preparing an alkali metal or alkaline earth metal hydroxide, wherein the alkali amount is 0.01-10 times of the molar amount of ethanolamine, the concentration of an aminoethanol solution is 0.01-2 mol/L, the oxidation reaction temperature is 0-100 ℃, the oxidation reaction time is 0.1-6 h, the oxidation reaction pressure is 0.1-1 Mpa, glycinate is acidified by common cheap acid such as sulfuric acid, hydrochloric acid or phosphoric acid to obtain glycine, the concentration of the acid is 0.1-10 mol/L, the acidification time is 0.1-2 h, and the acidification temperature is 0-100 ℃.
The method for synthesizing the glycine by the oxidation method has the advantages of high conversion rate, good selectivity, small catalyst consumption, difficult inactivation and the like.
Detailed Description
The present invention is illustrated below by way of specific examples, but the application of the present invention is not limited to the ranges listed in the examples.
Example 1
10M L0.5.5M monoethanolamine solution was placed in a stirred autoclave and 0.5g NaOH and 0.1g imidazole type ionic liquid ([ Emim [ ]) were added][FeCl4]) (ii) a Sealing the autoclave with O2Replacing air in the kettle for three times, and then filling oxygen of 0.5 Mpa; placing the reaction kettle in a stirring and heating controller, setting the temperature to be 50 ℃, standing to enable the temperature in the kettle to reach the target temperature, and starting stirring to start reaction; after reacting for 2h, the stirrer was closed, the pressure was released, and the reaction solution was transferred to a beaker. Under the real-time monitoring of a pH meter, the reaction solution is titrated by a sulfuric acid solution until the pH value reaches about 6.0. Recrystallizing the obtained reaction liquid by methanol to obtain the glycine product. The ionic liquid is dissolved in methanol and can be recycled through suspension evaporation and concentration.
The product is subjected to nuclear magnetism qualitative and quantitative determination, and the conversion rate of the monoethanolamine is determined to be more than 95 percent, and the yield of the sodium glycinate is determined to be 85 percent.
Example 2
10M of L0.5.5M monoethanolamine solution was placed in a pressure vessel with stirring, and 0.5g NaOH and 0.1g quaternary ammonium type ionic liquid ([ N ] N) were added2224][CuCl2]) (ii) a Sealing the autoclave with O2Replacing air in the kettle for three times, and then filling oxygen of 0.5 Mpa; placing the reaction kettle in a stirring and heating controller, setting the temperature to be 50 ℃, standing to enable the temperature in the kettle to reach the target temperature, and starting stirring to start reaction; after reacting for 2h, the stirrer was closed, the pressure was released, and the reaction solution was transferred to a beaker. Under the real-time monitoring of a pH meter, the reaction solution is titrated by hydrochloric acid solution until the pH value reaches about 6.0. And recrystallizing the obtained reaction solution by using ethanol to obtain the glycine product. The ionic liquid is dissolved in ethanol and can be recycled through suspension evaporation and concentration.
The product is subjected to nuclear magnetism qualitative and quantitative determination, and the conversion rate of the monoethanolamine is determined to be more than 95 percent, and the yield of the sodium glycinate is determined to be 88 percent.
Example 3
10M L0.5.5M monoethanolamine solution was placed in a stirred autoclave, 0.5g NaOH and 0.1g quaternary amine type ionic liquid ([ N ] N2224][FeCl4]) (ii) a Sealing the autoclave with O2Replacing air in the kettle for three times, and then filling oxygen of 0.5 Mpa; placing the reaction kettle in a stirring and heating controller, setting the temperature to be 50 ℃, standing to enable the temperature in the kettle to reach the target temperature, and starting stirring to start reaction; after reacting for 2h, the stirrer was closed, the pressure was released, and the reaction solution was transferred to a beaker. Under the real-time monitoring of a pH meter, the reaction solution is titrated by a phosphoric acid solution until the pH value reaches about 6.0. And recrystallizing the obtained reaction solution by using ethanol to obtain the glycine product. The ionic liquid is dissolved in ethanol and can be recycled through suspension evaporation and concentration.
The product is subjected to nuclear magnetism qualitative and quantitative determination, and the conversion rate of the monoethanolamine is determined to be more than 95 percent, and the yield of the sodium glycinate is determined to be 80 percent.
Example 4
10M L0.5.5M monoethanolamine solution was placed in a stirred autoclave and 0.5g NaOH and 0.1g imidazole type ionic liquid ([ Emim [ ]) were added][CuBr2]) (ii) a Sealing the autoclave with O2Replacing air in the kettle for three times, and then filling oxygen of 0.5 Mpa; placing the reaction kettle in a stirring and heating controller, setting the temperature to be 50 ℃, standing to enable the temperature in the kettle to reach the target temperature, and starting stirring to start reaction; after reacting for 2h, the stirrer was closed, the pressure was released, and the reaction solution was transferred to a beaker. Under the real-time monitoring of a pH meter, the reaction solution is titrated by a sulfuric acid solution until the pH value reaches about 6.0. Recrystallizing the obtained reaction liquid by methanol to obtain the glycine product. The ionic liquid is dissolved in methanol and can be recycled through suspension evaporation and concentration.
The product is subjected to nuclear magnetism qualitative and quantitative determination, and the conversion rate of the monoethanolamine is determined to be more than 95 percent, and the yield of the sodium glycinate is determined to be 90 percent.
Example 5
10M L0.5.5M monoethanolamine solution was placed in a stirred autoclave and 0.5g NaOH and 0.1g quaternary phosphonium type ionic liquid ([ P ] P) were added4444][AuCl4]) (ii) a Sealing the autoclave with O2Replacing air in the kettle for three times, and then filling 0.5MpaOxygen of (2); placing the reaction kettle in a stirring and heating controller, setting the temperature to be 50 ℃, standing to enable the temperature in the kettle to reach the target temperature, and starting stirring to start reaction; after reacting for 2h, the stirrer was closed, the pressure was released, and the reaction solution was transferred to a beaker. Under the real-time monitoring of a pH meter, the reaction solution is titrated by a sulfuric acid solution until the pH value reaches about 6.0. Recrystallizing the obtained reaction liquid by methanol to obtain the glycine product. The ionic liquid is dissolved in methanol and can be recycled through suspension evaporation and concentration.
The product is subjected to nuclear magnetism qualitative and quantitative determination, and the conversion rate of the monoethanolamine is determined to be more than 95 percent, and the yield of the sodium glycinate is determined to be 83 percent.

Claims (9)

1. A method for preparing glycine by an oxidation method is characterized in that monoethanolamine solution and oxygen are used as reaction raw materials, and are reacted under the action of an ionic liquid catalyst and alkali to generate glycinate, and the glycinate is further obtained by the glycinate through an acidification process;
the cation of the ionic liquid catalyst is a polyalkyl-substituted imidazole, pyrrole, pyridine, piperidine, quaternary ammonium or quaternary phosphonium cation, wherein the length of an alkyl side chain is between 1 and 16; the anion of the ionic liquid catalyst is [ AuCl ]4]-、[FeCl4]-、[CoCl4]2-、[MoCl6]3-、[WCl6]-、[ZnCl4]2-、[AuClBr3]-、[FeClBr3]-、[CoClBr2]-、[ZnClBr2]-、[CuCl2]-、[CuBr2]-、[W2O11]2-、[HPW12O40]2-At least one of (1).
2. The method according to claim 1, wherein the amount of the ionic liquid catalyst is 0.1-50% of the molar amount of monoethanolamine.
3. The method of claim 1, wherein the base is an alkali metal hydroxide or an alkaline earth metal hydroxide.
4. The method according to claim 1, wherein the amount of the base is 0.01 to 10 times the amount of the monoethanolamine substance.
5. The method according to claim 1, wherein the concentration of the monoethanolamine solution is 0.01-2 mol/L.
6. The process according to claim 1, characterized in that the reaction is carried out under the following conditions: the temperature is 0-100 ℃, the pressure is 0.1-1 Mpa, and the time is 0.1-6 h.
7. The method of claim 1, wherein the acid used in the acidification process is sulfuric acid, hydrochloric acid or phosphoric acid.
8. The method according to claim 7, wherein the concentration of the acid is 0.1 to 10 mol/L.
9. The method according to claim 7, wherein the acidification temperature is 0-100 ℃ and the acidification time is 0.1-2 h.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107216262A (en) * 2017-04-18 2017-09-29 中国科学院过程工程研究所 A kind of method that homogeneous system intermediate ion liquid catalyst synthesizes glycine

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JP6327668B2 (en) * 2014-11-14 2018-05-23 株式会社日本触媒 High purity glycine salt and glycine, and method for producing the same
JP6553988B2 (en) * 2015-08-28 2019-07-31 株式会社日本触媒 Method for producing aminocarboxylic acid salt

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107216262A (en) * 2017-04-18 2017-09-29 中国科学院过程工程研究所 A kind of method that homogeneous system intermediate ion liquid catalyst synthesizes glycine

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A novel CuCl2/BIL catalyst for direct oxidation of alcohol to acid at ambient temperature;Parasuraman Karthikeyan等;《Catalysis Communications》;20120601;第26卷;第189页摘要，第190页右栏第2段 *
Efficient Copper-bisisoquinoline-based Catalysts for Selective Aerobic Oxidation of Alcohols to Aldehydes and Ketones;Hao-Yu Shen等;《Int.J.Mol.Sci.》;20070606;第8卷;第505-512页 *
改性Raney-Cu催化一乙醇胺脱氢合成甘氨酸;蔡振云 等;《精细化工》;20030331;第20卷(第3期);第187-189页 *
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