CN111018727A - Method for producing glycine - Google Patents
Method for producing glycine Download PDFInfo
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- CN111018727A CN111018727A CN201811175351.0A CN201811175351A CN111018727A CN 111018727 A CN111018727 A CN 111018727A CN 201811175351 A CN201811175351 A CN 201811175351A CN 111018727 A CN111018727 A CN 111018727A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
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Abstract
The invention relates to a production method of glycine. The method comprises the steps of contacting glycolic acid and an ammonia source with a catalyst; the catalyst comprises a carrier and a metal active component; the metal active component is at least one metal simple substance selected from the group consisting of Ru, Re, Rh, Pd, Pt, Co, Ni, Cu, Cr, Nb and Ir, an oxide thereof or a combination thereof.
Description
Technical Field
The invention relates to a production method of glycine.
Background
Glycine (or glycine), is the simplest of amino acids in the amino acid series. The molecule has both amino and carboxyl functional groups, so that the acid-base composite material has both acidity and alkalinity, and can be adjusted by acid and alkali to present different molecular forms. At present, glycine can be used for manufacturing herbicide glyphosate, can also be used as food and feed additives, and can also be used for synthesizing various medicaments. According to different production technology and product quality requirements of glycine, the glycine can be divided into four specifications of food grade, medicine grade, feed grade and industrial grade products. The technical routes for industrially producing glycine mainly comprise chloroacetic acid ammonolysis, Strecker, hydantoin and biological methods, wherein chloroacetic acid is mainly used as a raw material at home, and improved technical routes of the Strecker and hydantoin methods are adopted at foreign countries. The chloroacetic acid ammonolysis method is characterized in that chloroacetic acid and ammonia water are used as raw materials in a water phase or an alcohol phase, and the chloroacetic acid ammonolysis method is prepared under the action of a urotropine catalyst. Firstly, dissolving a catalyst in ammonia water, dropwise adding chloroacetic acid under good stirring, reacting for a period of time at a certain temperature, and then obtaining the industrial-grade glycine with the purity of about 95% by an alcohol precipitation method. The method has the advantages of easily obtained raw materials, simple synthesis process and low requirement on equipment. The disadvantages are longer reaction time, poorer product quality and high refining cost; and a large amount of wastewater rich in inorganic salt and formaldehyde can be generated, and the catalyst urotropine is difficult to recycle. According to the Schterek's method, a highly toxic cyanide is used as a raw material, a formaldehyde aqueous solution, sodium cyanide and ammonium chloride are mixed and then react at a low temperature, acetic acid is added after the reaction is finished to separate the iminoacetonitrile out, then the iminoacetonitrile is dissolved in ethanol, sulfuric acid is added to convert the iminoacetonitrile into aminoacetonitrile sulfate, and finally stoichiometric barium hydroxide is added to generate barium sulfate and glycine. In order to improve the quality of glycine, reduce cost and reduce environmental pollution, the improved Scherrer method takes hydrocyanic acid, formaldehyde, ammonia and carbon dioxide as raw materials, and reaction liquid is carried out in a tubular reactor. Glycine is precipitated at low temperature, and the mother liquor is recycled. Although the process flow is short and the yield is high, the production development of the glycine is restricted because the high-toxicity cyanide is adopted and cannot be transported for a long distance. The hydantoin method uses hydroxyacetonitrile as a raw material to replace highly toxic cyanide, and becomes one of the technological routes which are concerned abroad. The biological method takes the cyanamide as a raw material, and the cyanamide aqueous solution is subjected to hydrolysis reaction under the action of microbial enzyme, so that the cyanamide aqueous solution is converted into the glycine. However, this method is limited by the scale of the strain, the reaction time, the operation conditions, and the like.
Document CN106699583A discloses a glycine production process, in which chloroacetic acid, a catalyst and a multi-component solvent are added into a reactor by a halogenated acid method, liquid ammonia is introduced for a synthetic reaction by a circulation method, so as to obtain a mixed solution of glycine and ammonium chloride, the catalyst is recycled, and then an ionic membrane separation device is used to obtain ammonium chloride and glycine respectively. In contrast, the glycine production process disclosed in document CN106699589A obtains glycine and ammonium chloride crystals by using ceramic membrane separation, continuous chromatographic separation, concentration, crystallization and other schemes. Document CN105859571A uses an organic solvent to produce glycine, and ammonium chloride as a by-product is obtained by hot filtration and centrifugation. Document CN103242181A provides a clean production process of glycine, which can co-produce a triethylamine hydrochloride product while producing glycine. The product can be glycine, or mixed crystal of glycine and triethylamine hydrochloride, or triethylamine hydrochloride product can be obtained. The mixed crystal can be directly used for producing glyphosate or iminodiacetic acid.
Glycolic acid is a chemical that can be produced by coal chemical processes and can be used to produce high-end chemicals such as pharmaceutical materials, films, and the like. Since the glycolic acid has a structure similar to that of glycine, the glycolic acid can be converted into the glycine through amino grafting, and a feasible technical route is provided for the production of the glycine. Document US2004/0092725a1 discloses a process for the preparation of glycine starting from glycolic acid at elevated temperature and pressure without catalyst, using a temperature of at least 250 ℃ and a pressure of at least 20MPa, but with a very low yield of glycine. Only 4.3 percent of glycine is obtained under the conditions of 374 ℃ and 35MPa, and when the temperature is continuously increased to 400 ℃, the yield of the glycine is only 4.2 percent. The method is obviously not suitable for industrial amplification, and the subsequent purification and refining are difficult, so that the method has space for further development and improvement.
Disclosure of Invention
The invention aims to solve the technical problems of over high temperature and pressure and low glycine selectivity in the method for preparing glycine from glycolic acid in the prior art, and provides a novel catalytic glycine production process by taking glycolic acid as a raw material.
In particular, the invention relates to a production method of glycine. The method comprises the steps of contacting glycolic acid and an ammonia source with a catalyst; the catalyst comprises a carrier and a metal active component; the metal active component is at least one metal simple substance selected from the group consisting of Ru, Re, Rh, Pd, Pt, Co, Ni, Cu, Cr, Nb and Ir, an oxide thereof or a combination thereof.
According to one aspect of the invention, the metal active component is present in an amount of 0.1 to 35 wt%, preferably 1 to 30 wt%, preferably 3 to 30 wt%, and more preferably 3 to 20 wt%, based on the weight of the elemental metal, based on the support.
According to an aspect of the present invention, the metal active component is selected from at least one simple metal substance of the group consisting of Ru, Rh, Co, and Ni, an oxide thereof, or a combination thereof.
According to an aspect of the invention, the ammonia source is at least one selected from the group consisting of ammonia gas, aqueous ammonia, liquid ammonia, urea, ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium acetate, ammonium formate and ammonium propionate.
According to one aspect of the invention, the support is selected from the group consisting of SiO2、Al2O3Activated carbon, ZrO2、TiO2At least one of the group consisting of diatomaceous earth, molecular sieves, and carbon nanotubes; preferably selected from the group consisting of SiO2、Al2O3Activated carbon, ZrO2And TiO2At least one of the group consisting of.
According to one aspect of the invention, the molar ratio of the glycolic acid to the amino groups in the ammonia source is 1:1 to 10, preferably 1:1 to 6, more preferably 1:1 to 3; the amount of the catalyst is 0.5-20%, preferably 0.8-12%, more preferably 3-10% of the weight of glycolic acid.
According to one aspect of the invention, the conditions under which the glycolic acid and ammonia source are contacted with the catalyst include: the temperature is 60-220 ℃, preferably 80-180 ℃, and more preferably 100-170 ℃; the pressure is 0.1 to 5MPa, preferably 0.5 to 3MPa, and more preferably 1 to 2.5 MPa.
According to one aspect of the invention, the step of contacting the glycolic acid and the ammonia source with the catalyst is carried out in the presence of a solvent.
According to an aspect of the present invention, the solvent is at least one selected from the group consisting of dichloromethane, 1, 2-dichloroethane, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran and water; preferably water; the amount of the solvent is 2 to 100 times, preferably 5 to 50 times, and more preferably 5 to 20 times the volume of glycolic acid.
According to one aspect of the invention, the catalyst further comprises a promoter; the auxiliary agent is at least one metal simple substance selected from the group consisting of Mg, Zn, Fe, Ag, B, Li, Ga, La and Ce, an oxide thereof or a combination thereof; at least one simple metal selected from the group consisting of Mg, Zn and Fe, an oxide thereof or a combination thereof is preferable.
According to one aspect of the invention, the weight content of the auxiliary agent is 0 to 15%, preferably 1 to 10%, preferably 2 to 8%, and more preferably 2 to 5% based on the weight of the elemental metal and the carrier.
According to one aspect of the invention, the catalyst further comprises an additive; the additive is selected from the group consisting of NaBH4、KBH4、NaBH3CN and sodium triacetoxyborohydride; sodium triacetoxyborohydride is preferred.
According to one aspect of the invention, the additive is contained in an amount of 0 to 10%, preferably 0.1 to 8%, preferably 0.1 to 5%, more preferably 0.5 to 3% by mole of glycolic acid.
According to one aspect of the invention, the step of contacting the glycolic acid and the ammonia source with the catalyst is carried out in a reducing gas atmosphere.
According to one aspect of the invention, the reducing gas atmosphere comprises hydrogen, or a combination of hydrogen and CO.
According to one aspect of the invention, the reducing gas atmosphere further comprises a diluent gas, preferably nitrogen or argon, or a combination thereof, inert to the contact of the glycolic acid and ammonia source with the catalyst; argon is preferred.
According to one aspect of the invention, the volume percentage of the dilution gas in the reduction gas is not higher than 50%.
The invention has the beneficial effects that:
according to the invention, the reaction condition is mild, the temperature is 60-220 ℃, and the pressure is 0.1-5 MPa. In the prior art, the temperature is at least 250 ℃ and the pressure is at least 20 MPa.
According to the invention, the selectivity of the glycine can reach 45 percent, which is 10 times higher than that of the glycine without the catalyst.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, procedures, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently in use, but would become known in the art to be suitable for a similar purpose.
In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.
Any particular value disclosed herein (including endpoints of ranges of values) is not to be limited to the precise value of that value, but rather is to be understood to also encompass values close to the precise value, i.e., to be understood as modified by the term "about". Also, for the disclosed ranges of values, any combination between the endpoints of the ranges, between the endpoints and specific points within the ranges, and between specific points within the ranges can result in one or more new ranges of values, which should also be considered as specifically disclosed herein.
Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.
All pressures mentioned in this specification are, unless explicitly stated, gauge pressures.
According to the present invention, there is provided a process for producing glycine. The method includes the step of contacting glycolic acid and an ammonia source with a catalyst.
According to the invention, the catalyst is a supported catalyst containing one or more active components, comprising a support and a metal active component.
According to the present invention, the metal active component has hydrogenation and dehydrogenation functions, and is at least one metal simple substance selected from the group consisting of Ru, Re, Rh, Pd, Pt, Co, Ni, Cu, Cr, Nb, and Ir, an oxide thereof, or a combination thereof; at least one metal simple substance selected from the group consisting of Ru, Rh, Co and Ni, an oxide thereof or a combination thereof is preferable.
According to the invention, the weight content of the metal active component is 0.1-35%, preferably 1-30%, preferably 3-30%, more preferably 3-20% by weight of the elemental metal based on the carrier.
According to the invention, the catalyst comprises, in addition to the metal active component, an auxiliary agent. The auxiliary agent has the functions of strengthening the reaction process, promoting hydrogenation and dehydrogenation reactions and increasing the selectivity of glycine. The auxiliary agent is at least one metal simple substance selected from the group consisting of Mg, Zn, Fe, Ag, B, Li, Ga, La and Ce, an oxide thereof or a combination thereof; to reduce the catalyst cost, it is preferable to use a non-noble metal component, such as at least one metal selected from the group consisting of Mg, Zn and Fe, its oxide or a combination thereof.
According to the invention, the weight content of the auxiliary agent is 0-15%, preferably 1-10%, preferably 2-8%, more preferably 2-5% based on the weight of the elemental metal and based on the carrier.
According to the invention, the catalyst can also be added with NaBH on the basis of a supported catalyst4、KBH4、NaBH3CN and sodium triacetoxyborohydride. Due to glycolic acidAn intermediate product imine can be generated in the process of generating glycine through reaction, the imine generally has higher activity, and double bond hydrogenation of the imine can be realized by adopting a mild additive. After the catalyst is added with the additive with hydrogen supply function, the reaction process is milder. The additive is preferably mild sodium triacetoxyborohydride.
According to the invention, the content of the additive is 0 to 10%, preferably 0.1 to 8%, preferably 0.1 to 5%, more preferably 0.5 to 3% of the molar amount of glycolic acid.
According to the invention, the support is an inert or weakly acidic support selected from the group consisting of SiO2、Al2O3Activated carbon, ZrO2、TiO2At least one of the group consisting of diatomaceous earth, molecular sieves, and carbon nanotubes; preferably selected from the group consisting of SiO2、Al2O3Activated carbon, ZrO2And TiO2At least one of the group consisting of.
According to the present invention, the catalyst can be prepared by methods well known in the art, such as kneading, impregnation and precipitation, preferably impregnation or precipitation.
According to the invention, the catalyst is used in an amount of 0.5 to 20%, preferably 0.8 to 12%, more preferably 3 to 10% by weight of glycolic acid.
According to the present invention, the step of contacting the glycolic acid and the ammonia source with the catalyst is preferably carried out in the presence of a solvent. As a solvent, it cannot participate in the reaction, or can decompose under the reaction conditions. Methanol, ethanol, and the like contain the same alcoholic hydroxyl group as glycolic acid, and therefore cannot be used as a solvent for the reaction. The solvent is at least one selected from the group consisting of dichloromethane, 1, 2-dichloroethane, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran and water according to the characteristics of the reaction. Preferably, water is used as the solvent. The water can dissolve both the reactant and the product, and has no adverse effect on the environment. When water is used as a solvent, the raw material of glycolic acid can be dissolved in water and then conveyed into a reaction kettle through a feeding pump, so that continuous feeding is realized. The organic solvent such as dichloromethane, 1, 2-dichloroethane, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran and the like can be recovered by means of reduced pressure distillation and reused in the reaction process, so that the discharge of waste liquid is reduced.
According to the present invention, the amount of the solvent used is 2 to 100 times, preferably 5 to 50 times, and more preferably 5 to 20 times the volume of glycolic acid.
According to the invention, the source of ammonia is a gas containing NH3Or NH4 +Or an organic or inorganic compound capable of generating an amino group at a reaction temperature, for example, at least one selected from the group consisting of ammonia gas, aqueous ammonia, liquid ammonia, urea, ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium acetate, ammonium formate and ammonium propionate. When the ammonia source is gaseous ammonia, it may participate in regulating the pressure of the reaction. When the ammonia source is other liquid or salt or organic matter soluble in the solvent, it may be continuously fed into the reactor by a pump.
According to the present invention, the molar ratio of the glycolic acid to the amino group in the ammonia source is 1:1 to 10, preferably 1:1 to 6, and more preferably 1:1 to 3. By adjusting the proportion of the ammonia source, the generation of glycine is ensured, and the occurrence of side reactions is reduced. When the proportion of amino groups is too high, ammonia may be caused to react with the carboxyl groups to produce salts or further to produce a bisamino product. In addition, when the ammonia content is too high, the pH of the solution may rise, which may also lead to the formation of cyclic compounds. When the proportion of amino groups is too low, ammonia may be reacted with a plurality of glycolic acids.
According to the invention, a certain reaction temperature is required for the dehydrogenation of glycolic acid, but at a higher temperature, the product glycine is decomposed again, and more by-products are generated. Therefore, the reaction temperature is 60 to 220 ℃, preferably 80 to 180 ℃, and more preferably 100 to 170 ℃.
According to the invention, the step of contacting the glycolic acid and the ammonia source with the catalyst is carried out in a reducing gas atmosphere. The reducing gas atmosphere comprises hydrogen or CO, or a combination thereof. Pure hydrogen is preferred.
According to the invention, a certain reaction pressure can increase the solubility of gaseous hydrogen in reactants, but an excessively high reaction pressure does not have a strong promoting effect on the reaction, so that the reaction pressure is 0.1-5 MPa, preferably 0.5-3 MPa, and more preferably 1-2.5 MPa.
According to the present invention, when the reaction atmosphere is a reducing atmosphere containing hydrogen, CO or the like, N can be used2Argon or other inert gas, but the volume fraction of the hydrogen is not less than 50 percent, so as to ensure that the reaction can be carried out smoothly.
According to the present invention, the mixed solution containing glycine obtained can be purified by an alcohol precipitation method known in the art, and by a method such as distillation, extraction, membrane separation, etc., to obtain glycine having a high purity.
The invention is further illustrated by the following examples.
[ example 1 ]
50g of glycolic acid, 250mL of dichloroethane and Ru/SiO were added to the reaction kettle in this order20.5g of catalyst (3 wt% of Ru load) and 55g of 25 wt% ammonia water solution, uniformly stirring, slowly introducing hydrogen to the pressure of 1MPa, then heating the reaction kettle to 100 ℃, reacting for 2 hours, and cooling to finish the reaction.
The conversion of glycolic acid was 71.4% and the selectivity to glycine was 33.2%.
[ example 2 ]
50g of glycolic acid, 250mL of tetrahydrofuran and Ru/SiO are sequentially added into a reaction kettle20.5g of catalyst (3 wt% of Ru load) and 55g of 25 wt% ammonia water solution, uniformly stirring, slowly introducing hydrogen to the pressure of 1MPa, then heating the reaction kettle to 100 ℃, reacting for 2 hours, and cooling to finish the reaction.
The conversion of glycolic acid was 69.3% and the selectivity to glycine was 32.5%.
[ example 3 ]
50g of glycollic acid, 250mL of deionized water and Ru/SiO are sequentially added into a reaction kettle20.5g of catalyst (3 wt% of Ru load) and 55g of 25 wt% ammonia water solution, uniformly stirring, slowly introducing hydrogen to the pressure of 1MPa, then heating the reaction kettle to 100 ℃, reacting for 2 hours, and cooling to finish the reaction.
The conversion of glycolic acid was 65.2% and the selectivity to glycine was 33.4%.
[ example 4 ]
In the reaction kettle in turn50g of glycolic acid, 250mL of deionized water, Ru/SiO were added20.5g of catalyst (3 wt% of Ru load) and 55g of 25 wt% ammonia water solution, uniformly stirring, slowly introducing hydrogen to the pressure of 1MPa, then heating the reaction kettle to 160 ℃, reacting for 2 hours, and cooling to finish the reaction.
The conversion of glycolic acid was 82.1% and the selectivity to glycine was 40.4%.
[ example 5 ]
50g of glycollic acid, 250mL of deionized water and Ru/SiO are sequentially added into a reaction kettle20.5g of catalyst (3 wt% of Ru load) and 55g of 25 wt% ammonia water solution, uniformly stirring, slowly introducing hydrogen to the pressure of 1MPa, then heating the reaction kettle to 170 ℃, reacting for 2 hours, and cooling to finish the reaction.
The glycolic acid conversion was 89.2% and the glycine selectivity was 44.5%.
[ example 6 ]
45g of glycolic acid, 600mL of dichloromethane and Ru/Al were added to the reaction vessel in this order2O30.5g of catalyst (3 wt% of Ru load) and 50g of 25 wt% ammonia water solution are uniformly stirred, hydrogen is slowly introduced to the pressure of 1.5MPa, then the reaction kettle is heated to 150 ℃, and the reaction is finished after 2 hours of reaction and cooling.
The conversion of glycolic acid was 77.5% and the selectivity to glycine was 38.1%.
[ example 7 ]
45g of glycollic acid, 600mL of dichloromethane, 0.5g of Ru/kieselguhr catalyst (the load of Ru is 3 wt%) and 50g of 25 wt% ammonia water solution are sequentially added into a reaction kettle, the mixture is uniformly stirred, hydrogen is slowly introduced to the reaction kettle until the pressure is 1.5MPa, then the reaction kettle is heated to 150 ℃, and the reaction is finished after 2 hours of reaction and temperature reduction.
The conversion of glycolic acid was 71.3% and the selectivity to glycine was 35.2%.
[ example 8 ]
25g of glycollic acid, 350mL of deionized water, 1.0g of Ru-Co/active carbon catalyst (3 wt% of Ru and 5 wt% of Co), and 30g of ammonium carbonate are sequentially added into a reaction kettle, stirred uniformly, hydrogen is slowly introduced to the reaction kettle to reach the pressure of 2.1MPa, and then the reaction kettle is heated to 150 ℃ for reaction for 3 hours, and then the temperature is reduced to finish the reaction.
The conversion of glycolic acid was 80.9% and the selectivity to glycine was 39.2%.
[ example 9 ]
25g of glycollic acid, 350mL of deionized water, 1.0g of Ru-Co-Mg/active carbon catalyst (3 wt% of Ru load, 5 wt% of Co load and 2 wt% of Mg load) and 30g of ammonium carbonate are sequentially added into a reaction kettle, the mixture is uniformly stirred, hydrogen is slowly introduced to the reaction kettle until the pressure is 2.1MPa, then the reaction kettle is heated to 150 ℃, and the reaction is finished after 3 hours of reaction and cooling.
The conversion of glycolic acid was 82.3% and the selectivity to glycine was 40.1%.
[ example 10 ]
30g of glycollic acid, 34g of ammonium acetate and 200mL of deionized water are sequentially added into a reaction kettle, the mixture is uniformly stirred, 0.5g of Ru/carbon nano tube catalyst (the load of Ru is 5 wt%) is added, hydrogen is slowly introduced to the reaction kettle until the pressure is 1.5MPa, then the reaction kettle is heated to 120 ℃, and the reaction is finished after 3 hours of reaction and temperature reduction.
The conversion of glycolic acid was 72.5% and the selectivity to glycine was 40.2%.
[ example 11 ]
Adding 30g of glycolic acid, 30g of ammonia water and 200mL of deionized water into a reaction kettle in sequence, uniformly stirring, adding 0.5g of Ru/carbon nanotube catalyst (the load of Ru is 5 wt%), slowly introducing hydrogen to the pressure of 1.5MPa, then heating the reaction kettle to 120 ℃, reacting for 3 hours, and cooling to finish the reaction.
The conversion of glycolic acid was 74.4% and the selectivity to glycine was 40.8%.
[ example 12 ]
Adding 35g of glycolic acid, 64g of ammonium acetate and 250mL of deionized water into a reaction kettle in sequence, uniformly stirring, adding 0.5g of Ru-Fe/ZSM-5 catalyst (the load of Ru is 5 wt% and the load of Fe is 1 wt%), slowly introducing hydrogen to the pressure of 0.8MPa, continuously introducing CO to the pressure of 1.8MPa, subsequently heating the reaction kettle to 160 ℃, reacting for 2 hours, and cooling to finish the reaction.
The conversion of glycolic acid was 83.8% and the selectivity to glycine was 39.5%.
[ example 13 ]
Adding 35g of glycolic acid, 64g of ammonium acetate and 250mL of deionized water into a reaction kettle in sequence, uniformly stirring, adding 0.5g of Ru-Fe/ZSM-5 catalyst (the load of Ru is 5 wt% and the load of Fe is 1 wt%), slowly introducing hydrogen to the pressure of 0.8MPa, continuously introducing argon to the pressure of 1.8MPa, subsequently heating the reaction kettle to 160 ℃, reacting for 2 hours, and cooling to finish the reaction.
The conversion of glycolic acid was 83.1% and the selectivity to glycine was 38.3%.
[ example 14 ]
20g of glycollic acid and 400mL of 1, 2-dichloroethane are sequentially added into a reaction kettle, 0.2g of Ru/ZSM-5 catalyst (the load of Ru is 5 wt%) is added, the mixture is stirred uniformly, 6L of ammonia gas is slowly introduced, hydrogen gas is continuously introduced to the pressure of 2.8MPa, the reaction kettle is heated to 60 ℃, and the temperature is reduced after 5 hours of reaction to finish the reaction.
The conversion of glycolic acid was 27.2% and the selectivity to glycine was 33.7%.
[ example 15 ]
20g of glycollic acid and 400mL of 1, 2-dichloroethane are sequentially added into a reaction kettle, 0.2g of Ru/ZSM-5 catalyst (the load of Ru is 5 wt%) and 28g of sodium triacetoxyborohydride are added, the mixture is uniformly stirred, 6L of ammonia gas is slowly introduced, hydrogen gas is continuously introduced until the pressure is 2.8MPa, then the reaction kettle is heated to 60 ℃, and the reaction is finished after 5 hours of reaction and cooling.
The conversion of glycolic acid was 29.5% and the selectivity to glycine was 38.9%.
[ example 16 ]
20g of glycollic acid and 1000mL of 1, 2-dichloroethane are sequentially added into a reaction kettle, 0.2g of Ru/ZSM-5 catalyst (the load of Ru is 5 wt%) and 167g of sodium triacetoxyborohydride are added, the mixture is uniformly stirred, 6L of ammonia gas is slowly introduced, hydrogen gas is continuously introduced until the pressure is 2.8MPa, then the reaction kettle is heated to 60 ℃, and the reaction is finished after 5 hours of reaction and cooling.
The conversion of glycolic acid was 30.4% and the selectivity to glycine was 45.2%.
[ example 17 ]
20g of glycollic acid, 500mL of dichloromethane and 0.6g of Rh-Ce/activated carbon catalyst (the loading amount of Rh is 1 wt% and the loading amount of Ce is 2 wt%) are sequentially added into a reaction kettle, the mixture is uniformly stirred, then 7L of ammonia gas is slowly introduced, hydrogen gas is continuously introduced to the pressure of 2.5MPa, then the temperature of the reaction kettle is slowly raised to 160 ℃, and the reaction is finished after 2 hours of reaction and temperature reduction.
The glycolic acid conversion was 79.2% and the glycine selectivity was 43.9%.
[ example 18 ]
20g of glycollic acid, 500mL of dichloromethane and 0.6g of Rh-Ce/activated carbon catalyst (the loading amount of Rh is 1 wt% and the loading amount of Ce is 10 wt%) are sequentially added into a reaction kettle, the mixture is uniformly stirred, then 7L of ammonia gas is slowly introduced, hydrogen gas is continuously introduced to the pressure of 2.5MPa, then the temperature of the reaction kettle is slowly raised to 160 ℃, and the reaction is finished after 2 hours of reaction and temperature reduction.
The glycolic acid conversion was 87.6% and the glycine selectivity was 44.5%.
[ example 19 ]
30g of glycollic acid, 200mL of deionized water and Pd/TiO are added into a reaction kettle in sequence20.4g of catalyst (the load of Pd is 8 wt%), 35g of 25 wt% ammonia water solution, stirring uniformly, slowly introducing hydrogen to the pressure of 3MPa, then heating the reaction kettle to 120 ℃, reacting for 3 hours, and cooling to finish the reaction.
The conversion of glycolic acid was 67.3% and the selectivity to glycine was 32.6%.
[ example 20 ]
30g of glycollic acid, 200mL of deionized water and Pd/TiO are added into a reaction kettle in sequence20.4g of catalyst (the load of Pd is 8 wt%), 70g of 25 wt% ammonia water solution, stirring uniformly, slowly introducing hydrogen to the pressure of 3MPa, then heating the reaction kettle to 120 ℃, reacting for 3 hours, and cooling to finish the reaction.
The conversion of glycolic acid was 69.4% and the selectivity to glycine was 32.9%.
[ example 21 ]
40g of glycolic acid, 500mL of dichloromethane and Ni/Al were added to the reaction vessel in this order2O30.5g of catalyst (the load of Ni is 8 wt%), 55g of 25 wt% ammonia water solution, stirring uniformly, slowly introducing hydrogen to the pressure of 1.3MPa, and then heating the reaction kettle to the temperatureAnd (3) reacting at 150 ℃ for 2 hours, and then cooling to finish the reaction.
The conversion of glycolic acid was 61.8% and the selectivity to glycine was 38.3%.
[ example 22 ]
40g of glycolic acid, 500mL of dichloromethane and Ni/Al were added to the reaction vessel in this order2O30.5g of catalyst (the load of Ni is 18 wt%), 55g of 25 wt% ammonia water solution, stirring uniformly, slowly introducing hydrogen to the pressure of 1.3MPa, then heating the reaction kettle to 150 ℃, reacting for 2 hours, and cooling to finish the reaction.
The glycolic acid conversion was 73.6% and the glycine selectivity was 39.2%.
[ example 23 ]
40g of glycolic acid, 500mL of dichloromethane and Ni/Al were added to the reaction vessel in this order2O30.5g of catalyst (the load of Ni is 32 wt%), 55g of 25 wt% ammonia water solution, stirring uniformly, slowly introducing hydrogen to the pressure of 1.3MPa, then heating the reaction kettle to 150 ℃, reacting for 2 hours, and cooling to finish the reaction.
The glycolic acid conversion was 85.6% and the glycine selectivity was 42.4%.
[ example 24 ]
30g of glycollic acid, 300mL of deionized water and Ni-Zn/Al are sequentially added into a reaction kettle2O30.8g of catalyst (10 wt% of Ni load and 2 wt% of Zn load) and 100g of 25 wt% ammonia water solution, stirring uniformly, slowly introducing hydrogen to the pressure of 1.8MPa, then heating the reaction kettle to 210 ℃, reacting for 1.5 hours, and cooling to finish the reaction.
The conversion of glycolic acid was 95.9% and the selectivity to glycine was 35.4%.
[ example 25 ]
20g of glycolic acid, 300mL of 1, 2-dichloroethane, and Co-La/Al were added to the reaction vessel in this order2O30.3g of catalyst (8 wt% of Co and 2 wt% of La), stirring uniformly, then slowly introducing 6L of ammonia gas, continuously introducing hydrogen gas to the pressure of 3MPa, then slowly heating the reaction kettle to 150 ℃, reacting for 3 hours, and cooling to finish the reaction.
The conversion of glycolic acid was 66.4% and the selectivity to glycine was 38.3%.
[ example 26 ]
20g of glycolic acid, 300mL of 1, 2-dichloroethane and Co/Al were added to the reaction vessel in this order2O30.3g of catalyst (the load of Co is 8 wt%), stirring uniformly, then slowly introducing 6L of ammonia gas, continuously introducing hydrogen gas to the pressure of 3MPa, then slowly heating the reaction kettle to 150 ℃, reacting for 3 hours, and cooling to finish the reaction.
The conversion of glycolic acid was 62.8% and the selectivity to glycine was 36.5%.
[ example 27 ]
20g of glycolic acid, 300mL of 1, 2-dichloroethane and Co/Al were added to the reaction vessel in this order2O30.3g of catalyst (the load of Co is 8 wt%), stirring uniformly, then slowly introducing 6L of ammonia gas, continuously introducing hydrogen gas to the pressure of 5MPa, then slowly heating the reaction kettle to 150 ℃, reacting for 3 hours, and cooling to finish the reaction.
The conversion of glycolic acid was 63.7% and the selectivity to glycine was 36.9%.
[ example 28 ]
20g of glycolic acid, 500mL of dichloromethane and Ni-Cu/ZrO were added to the reaction vessel in this order24g of catalyst (10 wt% of Ni and 6 wt% of Cu), stirring uniformly, then slowly introducing 6L of ammonia gas, continuously introducing hydrogen gas to the pressure of 3MPa, then slowly heating the reaction kettle to 140 ℃, reacting for 3 hours, and cooling to finish the reaction.
The conversion of glycolic acid was 70.2% and the selectivity to glycine was 38.5%.
[ example 29 ]
25g of glycolic acid, 30g of ammonium carbonate and 300mL of 1, 2-dichloroethane are sequentially added into a reaction kettle, the mixture is stirred uniformly, and then Ni-Co/Al is added2O31.2g of catalyst (8 wt% of Ni and 4 wt% of Co), slowly introducing hydrogen to the pressure of 2.1MPa, heating the reaction kettle to 140 ℃, reacting for 2 hours, and cooling to finish the reaction.
The conversion of glycolic acid was 62.1% and the selectivity to glycine was 37.2%.
[ example 30 ]
20g of glycollic acid, 400mL of deionized water, 3g of Co-Cu/ZSM-35 catalyst (6 wt% of Co load and 1 wt% of Cu load) and 50g of 25 wt% ammonia water solution are sequentially added into a reaction kettle, the mixture is uniformly stirred, hydrogen is slowly introduced to the reaction kettle until the pressure is 2.4MPa, then the reaction kettle is heated to 130 ℃, and the reaction is finished after 3 hours of reaction and cooling.
The conversion of glycolic acid was 61.2% and the selectivity to glycine was 35.1%.
Claims (17)
1. A process for the production of glycine comprising the steps of contacting glycolic acid and an ammonia source with a catalyst; the catalyst comprises a carrier and a metal active component; the metal active component is at least one metal simple substance selected from the group consisting of Ru, Re, Rh, Pd, Pt, Co, Ni, Cu, Cr, Nb and Ir, an oxide thereof or a combination thereof.
2. The production method of glycine as claimed in claim 1, wherein the weight content of the metal active component is 0.1-35%, preferably 1-30%, preferably 3-30%, more preferably 3-20% by weight of the elemental metal based on the carrier.
3. The method for producing glycine as claimed in claim 1, wherein the metal active component is selected from at least one metal simple substance selected from the group consisting of Ru, Rh, Co and Ni, an oxide thereof or a combination thereof.
4. The method for producing glycine according to claim 1, wherein said ammonia source is at least one selected from the group consisting of ammonia gas, aqueous ammonia, liquid ammonia, urea, ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium acetate, ammonium formate and ammonium propionate.
5. Process for the production of glycine according to claim 1 wherein the support is selected from the group consisting of SiO2、Al2O3Activated carbon, ZrO2、TiO2Diatomaceous earth, molecular sieve and carbon nanotubeOne kind of the compound is used; preferably selected from the group consisting of SiO2、Al2O3Activated carbon, ZrO2And TiO2At least one of the group consisting of.
6. The method for producing glycine according to claim 1, wherein the molar ratio of glycolic acid to amino groups in the ammonia source is 1:1 to 10, preferably 1:1 to 6, more preferably 1:1 to 3; the amount of the catalyst is 0.5-20%, preferably 0.8-12%, more preferably 3-10% of the weight of glycolic acid.
7. The process for producing glycine as claimed in claim 1, wherein the conditions under which the glycolic acid and ammonia source are contacted with the catalyst comprise: the temperature is 60-220 ℃, preferably 80-180 ℃, and more preferably 100-170 ℃; the pressure is 0.1 to 5MPa, preferably 0.5 to 3MPa, and more preferably 1 to 2.5 MPa.
8. The process for producing glycine as claimed in claim 1, wherein the step of contacting glycolic acid and an ammonia source with a catalyst is carried out in the presence of a solvent.
9. The method for producing glycine as claimed in claim 8, wherein the solvent is at least one selected from the group consisting of dichloromethane, 1, 2-dichloroethane, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran and water; preferably water; the amount of the solvent is 2 to 100 times, preferably 5 to 50 times, and more preferably 5 to 20 times the volume of glycolic acid.
10. The process for the production of glycine as claimed in any one of claims 1 to 9 wherein the catalyst further comprises an auxiliary; the auxiliary agent is at least one metal simple substance selected from the group consisting of Mg, Zn, Fe, Ag, B, Li, Ga, La and Ce, an oxide thereof or a combination thereof; at least one simple metal selected from the group consisting of Mg, Zn and Fe, an oxide thereof or a combination thereof is preferable.
11. The production method of glycine as claimed in claim 10, wherein the weight content of the auxiliary agent is 0-15%, preferably 1-10%, preferably 2-8%, more preferably 2-5% based on the weight of the elemental metal.
12. The process for the production of glycine as claimed in any one of claims 1 to 11 wherein said catalyst further comprises an additive; the additive is selected from the group consisting of NaBH4、KBH4、NaBH3CN and sodium triacetoxyborohydride; sodium triacetoxyborohydride is preferred.
13. The method for producing glycine as claimed in claim 12, wherein the content of the additive is 0 to 10%, preferably 0.1 to 8%, preferably 0.1 to 5%, more preferably 0.5 to 3% by mole of glycolic acid.
14. The process for producing glycine as claimed in any one of claims 1 to 13, wherein the step of contacting glycolic acid and an ammonia source with a catalyst is carried out in a reducing gas atmosphere.
15. Process for the production of glycine as claimed in claim 14 wherein the reducing gas atmosphere comprises hydrogen or a combination of hydrogen and CO.
16. The process for the production of glycine as claimed in any one of claims 14 to 15 wherein said reducing atmosphere further comprises a diluent gas inert to the contact of said glycolic acid and ammonia source with the catalyst, preferably nitrogen or argon, or a combination thereof; argon is preferred.
17. The method for producing glycine as claimed in claim 16, wherein the volume percentage of the diluting gas in the reducing gas is not more than 50%.
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