WO2023198025A1

WO2023198025A1 - Synthesis method and synthesis device for organic nitrogen-containing compound

Info

Publication number: WO2023198025A1
Application number: PCT/CN2023/087512
Authority: WO
Inventors: 李光琴; 廖培森; 冼家慧; 李穗生; 张亚伟
Original assignee: 中山大学
Priority date: 2022-04-11
Filing date: 2023-04-11
Publication date: 2023-10-19

Abstract

The present invention relates to the field of organic synthesis, specifically to a synthesis method and synthesis device for an organic nitrogen-containing compound. Provided in the present invention is a synthesis method for an organic nitrogen-containing compound. In the method provided in the present invention, a porous carbon material is used as a catalyst, organic nitrogen-containing compounds such as an oxime, an amine, a nitrile and an amino acid are synthesized by means of an electro-catalysis method, byproducts are unlikely to generate, and the method is safe and environmentally friendly. Experiments show that organic nitrogen-containing compounds such as an amino acid, an oxime, an amine and a nitrile are successfully synthesized by using the method of the present invention, and the method has good Faraday efficiency and yield. In the present application, the synthesis of the above organic nitrogen-containing compounds can be realized by using nitrogen oxide waste gas or waste water as a raw material; and by converting the nitrogen oxide waste gas or waste water, the utilization of waste is realized, and the benefits are maximized. Further provided in the present invention is a synthesis device for an organic nitrogen-containing compound, which device is used for solving the defects of high energy consumption, long consumption time, and complex product separation and purification of existing synthesis methods.

Description

Synthetic method and device for organic nitrogen-containing compounds

This application is required to be submitted to the China Patent Office on April 11, 2022, with the application number 202210373919. The name of the invention is "A method for synthesizing amino acids"; it was submitted to the China Patent Office on April 11, 2022, and the application number is 202210373920.2. The name of the invention is "Method for producing amino acids from nitrogen oxide exhaust gas and wastewater"; it was submitted on November 14, 2022 China Patent Office, the application number is 202211418221.1, and the invention name is "A synthesis method of amino acids"; it was submitted to the China Patent Office on November 14, 2022, the application number is 202211421717.4, and the invention name is "A synthesis method of organic nitrogen-containing compounds" The priority of the Chinese patent application, the entire content of which is incorporated into this application by reference.

Technical field

The present invention relates to the field of organic synthesis, specifically to a synthesis method and synthesis device of organic nitrogen-containing compounds.

Background technique

Nitrogen oxides include NO ₂ , NO, N ₂ O, N ₂ O ₃ , N ₂ O ₄ , NO ₃ ^- , NO ₂ ^-, etc., which seriously harm the environment and human health. Today, modern industrial society produces a large amount of toxic and harmful nitrogen oxides, but in most cases, such nitrogen oxides are discharged into the environment without being effectively treated.

Traditional synthesis methods for fine chemicals such as amines, nitriles and amides already exist. For example, in organic solvents, amines can be reductively aminated by heating carbonyl compounds and ammonia under the action of hydrogen to obtain organic amines. Nitriles can be prepared by nucleophilic substitution reaction between aliphatic halogenated hydrocarbons or sulfonate esters and metal cyanide, or by dehydration and oxidation of aldoxime to synthesize nitriles. Amides can be produced by the action of acid chlorides and amines under alkaline conditions.

The disadvantages of these traditional methods are: (1) using a large amount of organic solvents, which is not economical and environmentally friendly; (2) the cost of nitrogen sources is high; (3) by-products are easily produced during the thermal catalysis process; (4) partial reactions Highly toxic metal cyanide and flammable and explosive hydrogen are used, making the production highly dangerous.

With the development of social economy, the content of nitrogen oxides in the atmosphere continues to increase. More than 95% of nitrogen oxides come from vehicle exhaust emissions and flue gas emissions from thermal power plants. Nitrogen oxide exhaust gas and wastewater seriously harm the environment and human health. In response to this current situation, the country has increased its efforts in governance. Currently, flue gas tail gas denitrification technologies mainly include liquid absorption methods, solid adsorption methods, and catalytic reaction methods. The liquid absorption method is currently the most widely used in industry. The absorption liquid is sodium carbonate. This is the result of comprehensive consideration of factors such as price, source, ease of operation, and absorption efficiency. However, the absorption efficiency is relatively low. The solid adsorption method mainly uses molecular sieves, peat, silica gel or activated carbon for adsorption. However, there are currently problems such as small adsorption capacity, troublesome desorption and regeneration, and may cause secondary pollution. The catalytic reaction method is to pass gas containing nitrogen oxides into reducing gases, such as hydrogen, methane, etc., and use a catalyst to assist in reduction, thereby converting nitrogen oxides into nitrogen gas. Although this method has good reduction effect, it consumes a lot of catalysts and reducing agents, easily produces secondary pollution gas, and its application is limited.

To sum up, the existing nitrogen oxide exhaust gas and wastewater treatment technology only uses simple absorption and conversion. By means of chemical or catalytic reduction, it is degraded into non-polluting products such as nitrogen, which are further discharged to achieve safe emissions. In this process, a large amount of energy is consumed and secondary pollution may occur.

Amino acids are the basic substances that make up the proteins required for animal nutrition, especially α-amino acids, which are the building blocks of peptides and proteins. They are the basis of living organisms, play an important role in living organisms, and have many potential uses. . For example, as animal feed additives, flavoring agents, biochemical reagents, pharmaceuticals and cosmetics, etc. At present, amino acids are mainly produced through microbial fermentation processes and protein hydrolysis. This method can produce 20 kinds of amino acids that make up proteins, but the production efficiency is low. In addition, the fermentation process has potential problems such as strict requirements on aseptic operating conditions, long time consumption, high energy consumption of microbial culture, and complex product separation and purification processes.

Chemical synthesis is an effective method for synthesizing amino acids. The most common one is the Strecker reaction. This method generally uses aldehydes or ketones to react with hydrocyanic acid, cyanide, and amines to obtain α-aminonitriles, which are then hydrolyzed to obtain the corresponding aminonitriles. α-amino acids. This method has a relatively simple and mature process, a short reaction time, a small amount of waste liquid produced, and a product yield of about 70%. However, it requires the use of highly toxic cyanide, which poses a problem of high environmental pressure. The reaction route of Strecker reaction is as follows:

In addition, there is also the α-position oxime/nitrosation reduction method. This method generally uses carbonyl carboxylate to directly react with ammonia or hydroxylamine to generate an unstable imino carboxylate, and uses platinum and palladium as catalysts to catalyze the reduction of nitrosation. Amino carboxylic acid esters can obtain the corresponding amino acids, or amine ester compounds can be obtained by reduction with formic acid/zinc powder. The reaction route of the α-position oxime/nitrosation reduction method is as follows:

Furthermore, the reductive amination of α-keto acids is an excellent synthetic method that does not require the consumption of any toxic reagents. This method consists of two steps: ① condensation of carbonyl compounds with nitrogen sources (NH ₃ and NH ₂ OH) to obtain nitrogen-containing intermediates (such as imines and oximes); ② subsequent reductive hydrogenation of nitrogen-containing intermediates to form α-amino acids. The reductive amination reaction scheme of α-keto acids is as follows:

At present, the main methods for synthesizing amino acids are microbial fermentation, Strecker reaction and reductive amination of α-keto acids. All of the above methods have certain shortcomings and limitations. For example, the microbial fermentation process has major shortcomings such as strict requirements for aseptic operating conditions, high energy consumption and long time consumption of microbial culture, and complex product separation and purification processes. The Strecker reaction uses highly toxic cyanide, which puts great pressure on environmental protection. The α-site oxime/nitrosation reduction method and the reductive amination reaction of α-keto acid generally require toxic metals (lead, mercury) and noble metal catalysts.

Different from the traditional method of synthesizing amino acids, the electrocatalytic method of synthesizing amino acids can overcome the above shortcomings. However, there has been no research in this field, and the applied electrocatalysts are rarely reported. Traditional electrochemical catalysts generally need to support the catalyst material on the electrode through a Nafion binder. Due to the addition of the binder, the catalyst will inevitably be wrapped, leaving relatively few active sites exposed, thus affecting the catalytic performance; At the same time, the catalyst is only physically loaded through the adhesion of the binder. During the long-term electrocatalytic process or the catalytic process at a higher potential, it is easy to fall off from the electrode, resulting in a reduction in catalytic activity or even deactivation. .

At present, different catalysts are used for electrocatalytic synthesis of amino acids, but they are all amino acid synthesis routes that use hydroxylamine and other reaction materials as less difficult reaction materials. High Faradaic efficiency can be achieved by using a large excess of reaction materials such as hydroxylamine. Not only is the cost high but also a waste of resources, and the purity of the final amino acids obtained is also low.

Contents of the invention

In view of this, the technical problem to be solved by the present invention is to provide a method for synthesizing amino acids, which is used to solve the defects of high energy consumption, long time consumption, and complicated product separation and purification existing in the existing methods for synthesizing amino acids.

The technical problem to be solved by the present invention is to provide a method for synthesizing organic nitrogen-containing compounds. The method provided by the present invention can synthesize organic nitrogen-containing compounds such as oximes, amines and nitriles through electrocatalytic methods, and is not likely to produce by-products. Safe and environmentally friendly.

The invention provides a synthesis method of organic nitrogen-containing compounds, which includes the following steps:

Under the action of a catalyst, carbonyl compounds are used as carbon sources and at least one of nitrogen oxides or nitrogen hydrides is used as nitrogen sources to synthesize organic nitrogen-containing compounds through electrocatalysis; the catalyst includes porous carbon materials.

Specifically, the present invention uses the catalyst as a working electrode, a silver/silver chloride electrode as a reference electrode, a platinum electrode as a counter electrode, and the carbon source and nitrogen source as the electrolyte to perform an electrocatalytic reaction, Organic nitrogen-containing compounds are obtained.

In some embodiments of the present invention, the catalyst is used as the working electrode, the silver/silver chloride electrode is used as the reference electrode, the platinum electrode is used as the counter electrode, and the electrolyte solution, the carbon source and the nitrogen source are used as the electrolytic solution. liquid, perform electrocatalytic reaction, and obtain organic nitrogen-containing compounds; the electrolyte solution is selected from at least one of hydrochloric acid or potassium hydroxide; the concentration of the electrolyte solution is 0.1 mol/L to 2 mol/L.

In one embodiment, in an electrolytic cell provided with an anode chamber and a cathode chamber, the catalyst is used as a working electrode, and a silver/silver chloride electrode is used as a reference electrode. The working electrode and the reference electrode are in the In the cathode chamber; a platinum electrode is used as the counter electrode, and the counter electrode is in the anode chamber; an anode chamber electrolyte is added to the anode chamber, and a cathode chamber electrolyte is added to the cathode chamber to perform an electrocatalytic reaction , obtaining organic nitrogen-containing compounds; the cathode chamber electrolyte includes an electrolyte solution, the carbon source and a nitrogen source, the anode chamber electrolyte includes an electrolyte solution, the electrolyte solution in the cathode chamber electrolyte and the anode chamber The electrolyte solution in the electrolyte solution is the same; the electrolyte solution is the same as above and will not be described again.

The catalyst of the present invention includes porous carbon materials. The inventor of the present application creatively discovered that using the porous carbon material as a catalyst, organic nitrogen-containing compounds can be obtained by electrocatalyzing carbon sources and nitrogen sources. In some embodiments of the present invention, the total pore volume of the porous carbon material is 0.01cm ³ /g ~ 5.0cm ³ /g, and the specific surface area is 10m ² /g ~ 4000m ² /g. In some embodiments of the present invention, the porous carbon material is a porous carbon self-supporting material; the porosity of the porous carbon material is 0% to 99.9%; the pore size of the porous carbon material is 0 nm to 100 nm; The specific surface area of the porous carbon material is 10 m ² /g ~ 4000 m ² /g. In some embodiments of the present invention, the porous carbon material is selected from at least one of carbon fiber cloth, polyacrylonitrile membrane, and carbon fiber membrane.

The catalyst of the present invention may optionally include or not include supports. In some embodiments of the present invention, the catalyst of the present invention includes a porous carbon material and a load supported on the porous carbon material; the load is selected from at least one of metal organic framework materials and metals. In some embodiments of the present invention, the metal organic framework material is selected from at least one of ZIF series materials, MET series materials, MIL series materials, PCN series materials, UIO series materials, UMCM series materials or MOF series materials. ; Wherein, the ZIF series material is selected from at least one of ZIF-7, ZIF-8, and ZIF-67; the MET series material is selected from at least one of MET-3, MET-4, and MET-6. ; The MIL series materials are selected from at least one of MIL-53, MIL-88B, and MIL-125; the PCN series materials are selected from at least one of PCN-221, PCN-222, and PCN-224; the The UIO series materials are selected from at least one of UIO-66, UIO-67, and UIO-77; the UMCM series materials are selected from at least one of UMCM-9, UMCM-309, and UMCM-1; the MOF The series of materials is preferably selected from at least one of MOF-5, MOF-74, and MOF-177. In certain embodiments of the invention, the metal is selected from the group consisting of magnesium, manganese, iron, cobalt, nickel, copper, zinc, titanium, vanadium, chromium, molybdenum, ruthenium, rhodium, palladium, silver, bismuth, zirconium, cerium at least one of them.

The catalyst of the present invention may also include non-metal elements doped in the porous carbon material; the non-metal elements are selected from at least one of N, O, F, B, P, and S.

In some embodiments, the catalyst is selected from at least one of carbon fiber cloth, ZIF-8 supported polyacrylonitrile membrane (ZIF-8/PAN membrane), CoFe alloy supported carbon fiber membrane (CoFe-SSM membrane) . The carbon fiber cloth of the present invention is a carbon cloth well known to those skilled in the art and can be purchased in the market.

The present invention uses a carbonyl compound as a carbon source. During the electrocatalysis process, the carbonyl group in the carbonyl compound will be attacked by a nucleophile, thereby obtaining an organic nitrogen-containing compound. In certain embodiments of the invention, the carbonyl compound is selected from the group consisting of aldehydes, ketones, carboxylic acids, diketones, ketoacids, aminoketones, hydroxyketones or ketones At least one kind of ether compounds. In certain embodiments of the invention, the carbonyl compound is selected from the group consisting of acetone, benzaldehyde, butanone, 3-methyl-2-oxobutyric acid, 4-methyl-2-oxopentanoic acid, and α-diketone , at least one of α-keto acid, α-dialkylaminoketone, α-hydroxyketone or β-ketoether. In some embodiments, the concentration of the carbon source is above 0.1 mmol/L. In one embodiment, the concentration of the carbon source is 0.1 mmol/L to 1000 mmol/L. In one embodiment, the concentration of the carbon source is 0.1 mmol/L to 400 mmol/L. In one embodiment, the concentration of the carbon source is 0.1 mmol/L to 100 mmol/L.

The present invention uses at least one of nitrogen oxides or nitrogen hydrides as the nitrogen source. In the process of electrocatalysis, if nitrogen oxide is used as the nitrogen source, the nitrogen oxide will first be electrically reduced to nitrogen hydride, and then used as a nucleophile to attack the carbonyl group of the above carbonyl compound; if nitrogen hydride is used as the nitrogen source , then the nitrogen hydride will directly act as a nucleophile to attack the carbonyl group of the above carbonyl compound. In some embodiments of the present invention, the nitrogen oxide is selected from at least one of NO ₂ , NO, N ₂ O, N ₂ O ₃ , N ₂ O ₄ , NO ₃ ^- and NO ₂ ^- ; The nitrogen hydride is selected from at least one of NH ₂ OH, NH ₃ and NH ₄ ⁺ .

The nitrogen source of the present invention can participate in the process of electrocatalytically synthesizing organic nitrogen-containing compounds in the form of gas or liquid. In some embodiments of the present invention, the nitrogen source is a gas, and the flow rate of the nitrogen source is above 1 sccm. In some embodiments of the present invention, the nitrogen source is liquid, and the concentration of the nitrogen source is 0.001 mol/L to 100 mol/L. In one embodiment, the nitrogen source is gas, and the flow rate of the nitrogen source is 1 sccm to 20 sccm. In one embodiment, the nitrogen source is liquid, and the concentration of the nitrogen source is 0.001 mol/L to 1000 mmol/L. In one embodiment, the nitrogen source is liquid, and the concentration of the nitrogen source is 0.001 mol/L to 500 mmol/L.

In the present invention, under the action of the above catalyst, the above carbon source and nitrogen source are electrocatalytically reacted to synthesize organic nitrogen-containing compounds. In some embodiments of the present invention, the voltage of the electrocatalysis is 5V vs. RHE ~ -5V vs. RHE. In one embodiment, the voltage of the electrocatalysis is 0V vs. RHE ~ -3V vs. RHE. In one embodiment, the voltage of the electrocatalysis is 0V vs. RHE ~ -1.5V vs. RHE.

Through the method of the present invention, a variety of organic nitrogen-containing compounds can be synthesized. In certain embodiments of the present invention, the organic nitrogen-containing compound is selected from at least one of oxime, amine, and nitrile.

Among the above-mentioned organic nitrogen-containing compounds, oxime, as an important organic reaction intermediate, can be used to prepare compounds such as amines, amides, oxazoles, pyridines, nitrones, nitriles, and oxime ethers through thermal catalysis or electrocatalysis. In the present invention, on the cathode side of the electrolytic cell, nitrogen oxides are first electrically reduced to form NH ₂ OH, and then the NH ₂ OH is used as a nucleophile to attack the carbonyl group in the carbonyl compound to obtain a stable oxime as the product output. In embodiments, the organic nitrogen-containing compound is selected from acetone oxime, butanone oxime or benzaldehyde oxime.

Among the above-mentioned organic nitrogen-containing compounds, for amines, the present invention first electro-reduces nitrogen oxides to form NH ₃ or NH ₂ OH on the cathode side of the electrolytic cell, and then the NH ₃ or NH ₂ OH acts as a nucleophilic The reagent attacks the carbonyl group in the carbonyl compound to obtain intermediates such as imines or oximes, and then the intermediates such as imines or oximes are electroreductively hydrogenated to form amines. In embodiments, the organic nitrogen-containing compound is selected from benzylamine or furfurylamine.

Among the above-mentioned organic nitrogen-containing compounds, for nitriles, the present invention can first electrically reduce nitrogen oxides to form NH ₂ OH on the cathode side of the electrolytic cell, and then use the NH ₂ OH as a nucleophile to attack the carbonyl compounds. The carbonyl group obtains an oxime intermediate, which subsequently generates a nitrile under the action of a Lewis acid or a protonic acid without electrocatalysis. In embodiments, the organic nitrogen-containing compound is selected from isobutyronitrile and isovaleronitrile.

Among the above-mentioned organic nitrogen-containing compounds, for amides, the present invention can first electrically reduce nitrogen oxides to form NH ₂ OH on the cathode side of the electrolytic cell, and then use the NH ₂ OH as a nucleophile to attack the carbonyl compound. The carbonyl group is converted into an oxime, and the amide can be obtained through acidic Beckmann rearrangement without electrocatalysis. In the present invention, on the cathode side of the electrolytic cell, nitrogen oxides are first electrically reduced to form NH ₃ or NH ₂ OH, and then the NH ₃ or NH ₂ OH is used as a nucleophile to attack the carbonyl group to obtain intermediates such as imines or oximes. Subsequently, the amide is obtained by changing the conditions, electrocatalysis or thermal catalysis.

When the above catalyst includes a porous carbon material and a support supported on the porous carbon material, and the porous carbon material is a porous carbon self-supporting material, the preparation method includes: mixing a metal source and a carbon source, and performing electrospinning Silk, the product obtained after electrospinning is heat treated to obtain the above catalyst. In some embodiments, the preparation method of the above-mentioned catalyst includes: mixing a metal source and a carbon source, performing electrospinning, pre-oxidizing the product obtained after electrospinning, and then calcining to obtain the above-mentioned catalyst.

In one embodiment, the metal source is selected from metal organic frameworks, metal salts or MOF materials; the MOF material is loaded with metal salts or metal particles; the metal is selected from magnesium, manganese, iron, cobalt, nickel, copper , at least one of zinc, titanium, vanadium, chromium, molybdenum, ruthenium, rhodium, palladium, silver, bismuth, zirconium, and cerium. In one embodiment, the carbon source is selected from at least one of polyacrylonitrile, polyvinylidene fluoride, and polylactic acid. In one embodiment, the temperature of the pre-oxidation treatment is 150°C~350°C; the time of the pre-oxidation treatment is 30min~48h; the temperature of the calcination is 500°C~1200°C; the time of the calcination is 30min～12h.

The above-mentioned metal source can also be a metal source compounded with non-metal elements. The prepared catalyst includes a porous carbon material, a metal supported on the porous carbon material and a non-metal element doped in the porous carbon material. The porous carbon material is a porous carbon self-supporting material. In some embodiments of the present invention, the preparation method of the metal source compounded with non-metal elements includes: mixing the metal source, sodium citrate dihydrate and the non-metal source, and reacting to obtain a metal compound compounded with non-metal elements. source. Specifically, the preparation method of the metal source compounded with non-metal elements includes: mixing the metal source and sodium citrate dihydrate to obtain a mixed solution, adding the non-metal source solution into the mixed solution, and stirring for 5 to 15 minutes. Let the reaction stand for 6 to 30 hours to obtain a metal source compounded with non-metal elements. In one embodiment, the non-metal source is selected from at least one of N source, O source, F source, B source, P source and S source. The metal source is the same as above and will not be described again. In one embodiment, the non-metal source is selected from N sources, the N source is selected from potassium ferricyanate, and the preparation method of the metal source compounded with non-metal elements includes: combining the metal source and citric acid dihydrate Mix sodium to obtain a mixed solution, add potassium ferricyanate to the mixed solution, and stir for 5 After 15 min to 15 min, the reaction was left to react for 6 h to 30 h to obtain a metal source composite nitrogen-doped Prussian blue analogue (PBA).

The invention provides a method for synthesizing organic nitrogen-containing compounds, which includes the following steps: under the action of a catalyst, carbonyl compounds are used as carbon sources, and at least one of nitrogen oxides or nitrogen hydrides is used as nitrogen sources. Catalytically synthesizes organic nitrogen-containing compounds; the catalyst includes porous carbon materials. Under the action of a catalyst, the present invention can catalytically convert cheap and easily available inorganic nitrogen oxides and carbonyl compounds into organic carbon-nitrogen fine chemicals or pharmaceutical intermediates, such as oximes, amines, amides, nitriles, etc., through the electrocatalytic method. Organic nitrogen-containing compounds are not likely to produce by-products, and most of the present invention is carried out in a water system, which is safe and environmentally friendly. The present invention is expected to be used as a means to effectively reduce the environmental pollution caused by nitrogen oxides and to become a method for treating waste gas and waste water, thereby effectively solving the pollution problem of nitrogen oxides. Experiments show that organic nitrogen-containing compounds such as oximes, amines and nitriles are successfully synthesized through the method of the present invention, in which the yield of acetone oxime is 41.6% and the Faraday efficiency is 4.11%; the yield of butanone oxime is 53.3% and the Faraday efficiency is 53.3%. The efficiency is 9.61%; the yield of benzaldehyde oxime is 58.9%, and the Faradaic efficiency is 20.11%; the yield of benzylamine is 25.6%, and the Faradaic efficiency is 74.35%; the yield of furfurylamine is 25.91%, and the Faradaic efficiency is 20.6% ; The yield of isobutyronitrile is 25.3%, and the Faradaic efficiency is 9.79%; the yield of isovaleronitrile is 18.1%, and the Faradaic efficiency is 4.95%.

This application provides a method for synthesizing amino acids, including the following steps:

Under the action of porous carbon material catalysts, alpha-keto acid compounds are used as carbon sources and nitrogen oxides are used as nitrogen sources, and organic nitrogen compounds are synthesized through electrocatalysis.

In another embodiment, the total pore volume of the porous carbon material catalyst is 0.05-5.0 cm ³ /g, and the specific surface area is greater than 100-4000 m ² /g.

In another embodiment, the α-keto acid compounds include pyruvic acid, 4-hydroxyphenylpyruvic acid, 3-hydroxypyruvic acid, 3-thiopyruvic acid, 3-methyl-2-oxobutyric acid, 3 -Indolepyruvate, imidazole-4-pyruvate, 2-butyruvic acid, 6-amino-2-oxohexanoic acid, 4-(methylthio)-2-oxo-butyric acid, 3-hydroxy- 2-Oxo-butyric acid, 4-amino-2,4-dioxobutyric acid, 5-amino-2,5-dioxopentanoic acid, 5-[diaminomethylene]amino]-2- Oxopentanoic acid, 3-methyl-2-oxopentanoic acid, 4-methyl-2-oxopentanoic acid, phenylpyruvic acid, glyoxylic acid, oxaloacetic acid, alpha-ketoglutarate and 2-butanic acid One or more keto acids.

More specifically, the α-keto acid compounds include pyruvic acid, 3-methyl-2-oxopentanoic acid, 3-methyl-2-oxopentanoic acid, 4-methyl-2-oxopentanoic acid, benzene One or more of pyruvic acid, glyoxylic acid, oxaloacetic acid, α-ketoglutarate and 2-butyruvic acid.

In another embodiment, the nitrogen oxides are selected from NO, NO ₂ , NO ₂ ^- , NO ₃ ^- , N ₂ O, NH ₃ , NH ⁴⁺ , NH ₂ OH, nitrate nitrogen and nitrite nitrogen, one or more of them.

In another embodiment, the concentration of the α-keto acid compound is greater than or equal to 5mM, and the synthesis reaction of amino acids can be initiated at a concentration greater than or equal to this.

Specifically, the concentration of the α-keto acid compound is 0.005-1000M.

In another embodiment, when the nitrogen oxide is a gas, the flow rate of the nitrogen oxide is greater than or equal to 10 mL min ^-1 , and the synthesis reaction of amino acids can be started at a flow rate greater than or equal to this.

Specifically, when the nitrogen oxide is a gas, the flow rate of the nitrogen oxide is 0.01-1000L min _- ¹ .

In another embodiment, when the nitrogen oxide is liquid, the concentration of the nitrogen oxide is greater than or equal to 5mM, and the synthesis reaction of amino acids can be started at a concentration greater than or equal to this.

Specifically, when the nitrogen oxide is liquid, the concentration of the nitrogen oxide is 0.005-1000M.

In another embodiment, the voltage range of the electrocatalysis is -0.1V vs.RHE to -5.0V vs.RHE.

Specifically, when the catalyst, carbon source and nitrogen source are sufficient, the electrocatalysis of the synthesis method of the present application can be continued without time limit.

In another embodiment, the organic nitrogen compound includes one or more of amino acids, organic oximes, organic amines and amides; the amino acids are selected from the group consisting of glycine, alanine, valine, leucine, iso- Leucine, methionine, proline, tryptophan, serine, tyrosine, cysteine, phenylalanine, asparagine, glutamine, threonine, aspartic acid, One or more of glutamic acid, lysine, arginine, histidine, selenocysteine, and pyrrolysine.

The synthesis method of this application mainly uses amino acids.

It should be noted that the present application found that the porous carbon material catalyst has the function of electrocatalyzing the synthesis of amino acids. The porous carbon material catalyst required for the amino acid synthesis method provided by the present application can be an existing commercially available conventional porous carbon material catalyst, and can be a metal. Materials such as organic framework materials and nitrogen-containing metal-organic framework materials can also be porous carbon skeletons loaded with heteroatoms or/and multi-metal atoms. The porous carbon material catalysts are further limited and described below.

In another embodiment, the porous carbon material catalyst includes a porous carbon skeleton and heteroatoms or/and multi-metal atoms distributed in the porous carbon skeleton. The porous carbon skeleton mainly includes micropores, mesopores and macropores. Carbon structural material, the heteroatom is selected from one or more of N, O, S and P, the multi-element metal atom is selected from Al, Cu, Mn, Co, Ni, Mg, Fe, Zn, Pt, One or more of Pd, Ag, Au and Ru.

In another embodiment, the preparation method of the porous carbon material catalyst includes:

The nitrogen-containing metal-organic framework material is calcined under a protective atmosphere to obtain a porous carbon material catalyst; wherein the nitrogen-containing metal-organic framework material is selected from MET-6, ZIF-8, ZIF-67, MOF-74, PPy One or more of @MOF, PDA@MOF, HKUST-1, PCN series, MIL series, UiO series and UCM series.

In another embodiment, the preparation method of MET-6 includes:

Step 1. Mix soluble zinc salt, additives and amide compounds to obtain a mixture;

Step 2: Mix the mixture with 1H-1,2,3-triazole ligand to obtain MET-6.

In another embodiment, in step 1, the soluble zinc salt is selected from zinc chloride or/and zinc nitrate; the auxiliary agent is selected from one or more of ethanol, water and ammonia; the amide compound One or more selected from N,N-dimethylformamide, N,N-diethylformamide and N,N-dimethylacetamide.

Specifically, the ammonia water is an aqueous solution containing 25% to 28% ammonia.

Specifically, in step 2, the mixing time is 20 to 30 hours. The mixing of steps 1 and 2 is done by stirring.

Specifically, step 2 also includes filtering the product after mixing the mixture with 1H-1,2,3-triazole ligand to obtain a solid product, washing and drying the solid product to prepare MET-6; The washing is done with ethanol, and the drying temperature is 60-90°C.

In another embodiment, before the calcination, the method further includes: mixing nitrogen-containing metal-organic framework materials, metal salts and solvents, filtering to obtain a solid, and drying the solid to obtain M@MOF;

The preparation method of the porous carbon material catalyst specifically includes: calcining the M@MOF under a protective atmosphere to obtain a porous carbon material catalyst doped with metal atoms;

The metal salt is selected from the group consisting of Al ³⁺ chloride, Al ³⁺ nitrate, Al ³⁺ acetate, Al ³⁺ sulfate, Cu ²⁺ chloride, Cu ²⁺ nitrate , Cu ²⁺ acetate, Cu ²⁺ sulfate, Mn ²⁺ chloride, Mn ²⁺ nitrate, Mn ²⁺ acetate, Mn ²⁺ sulfate, Co ²⁺ Chloride, Co ²⁺ nitrate, Co ²⁺ acetate, Co ²⁺ sulfate, Ni ²⁺ chloride, Ni ²⁺ nitrate, Ni ²⁺ acetate, Ni ²⁺ sulfate, Mg ²⁺ chloride, Mg ²⁺ nitrate, Mg ²⁺ acetate, Mg ²⁺ sulfate, Fe ²⁺ chloride, Fe ²⁺ nitrate , Fe ²⁺ acetate, Fe ²⁺ sulfate, Fe ^{3+ chloride, Fe 3+} ^nitrate , Fe ³⁺ acetate, Fe ³⁺ sulfate, Zn ²⁺ Chloride, Zn ²⁺ nitrate, Zn ²⁺ acetate, Zn ²⁺ sulfate, Zn ²⁺ chloride, Zn ²⁺ nitrate, Zn ²⁺ acetate, Zn ²⁺ sulfate, Pt ²⁺ chloride, Pt ²⁺ nitrate, Pt ²⁺ acetate, Pt ²⁺ chlorate, Pd ²⁺ chloride, Pd ²⁺ nitric acid Salt, Pd ²⁺ acetate, Pd ²⁺ chlorate, Ag ²⁺ chloride, Ag ²⁺ sulfate, Ag ²⁺ acetate, Ag ²⁺ sulfate, Au ^{3 +} chloride, Au ³⁺ sulfate, Au 3+ acetate, Au ³⁺ chlorate ^, Ru ³⁺ chloride, Ru ²⁺ sulfate, Ru ³⁺ acetic acid One or more of salts and chlorates of Ru ⁴⁺ ;

The solvent is selected from one or more of ethanol, methanol, N,N-dimethylformamide, chloroform, acetone, distilled water and tetrahydrofuran.

Specifically, mix soluble zinc salt, auxiliary agent and amide compound to obtain a mixture; mix the mixture with 1H-1,2,3-triazole ligand to obtain MET-6; mix the MET-6, One or more metal salts are mixed with a solvent and filtered to obtain a solid. The solid is dried to obtain M@MOF; the M@MOF is calcined in a protective atmosphere to obtain a porous carbon material catalyst doped with metal atoms.

Specifically, the mixing temperature of MET-6, metal salt and solvent is 60°C to 100°C, and the time is 6 to 10 hours.

Specifically, mix soluble zinc salt, auxiliary agent and amide compound to obtain a mixture; mix the mixture with 1H-1,2,3-triazole ligand to obtain MET-6; mix the MET-6 in Calcined under a protective atmosphere to obtain a catalyst for the synthesis of amino acids, which is a porous carbon material doped with nitrogen atoms.

Specifically, the Fe@MET-6 precursor nitrogen-containing metal-organic framework was calcined in a protective atmosphere to obtain an iron-doped porous carbon material catalyst.

Specifically, the Cu@MET-6 precursor nitrogen-containing metal-organic framework was calcined in a protective atmosphere to obtain a copper-doped porous carbon material catalyst.

Specifically, the Cu-Fe@MET-6 nitrogen-containing precursor metal-organic framework was calcined under a protective atmosphere to obtain a copper-iron doped porous carbon material catalyst.

Specifically, the Ni@MET-6 nitrogen-containing precursor metal-organic framework was calcined in a protective atmosphere to obtain a nickel-doped porous carbon material catalyst.

Specifically, the Ni-Pt@MET-6 nitrogen-containing precursor metal-organic framework was calcined under a protective atmosphere to obtain a nickel-platinum doped porous carbon material catalyst.

Specifically, the Fe-Al@MET-6 nitrogen-containing precursor metal-organic framework was calcined under a protective atmosphere to obtain an iron-aluminum doped porous carbon material catalyst.

In another embodiment, the calcination temperature is 600°C to 1500°C; the calcination time is 1h to 24h.

This application applies the principle of α-keto acid reductive amination reaction, uses a cheap porous nitrogen-doped carbon material catalyst doped with iron atoms as the catalyst, uses nitrogen oxide as the nitrogen source, and electrocatalytically reduces it to form NH ₃ or NH ₂ OH, coupled with α-keto acid and then reductively hydrogenated to form α-amino acid. This application avoids the use of highly toxic cyanide, toxic metals (lead, mercury) and precious metal catalysts, uses nitrogen oxides as nitrogen sources, and couples with α-keto acids to form amino acids.

This application provides a method for producing amino acids from nitrogen oxide exhaust gas and wastewater. It can convert nitrogen oxide exhaust gas and wastewater into amino acids through electrocatalysis, realize waste utilization, obtain higher value amino acids while degrading pollutants, and realize benefits. of maximization.

This application provides a method for producing amino acids from nitrogen oxide exhaust gas and wastewater, including:

Mix nitrogen source, alpha-keto acid compound and porous carbon material catalyst in an electrolytic cell, and after electrochemical reaction, amino acids are obtained;

The nitrogen source consists of waste gas containing nitrogen oxides or/and wastewater containing nitrogen oxides.

Specifically, the synthesis route of the present application for producing amino acids from nitrogen oxide waste gas and waste water is as follows. N _x O _y is the waste gas containing nitrogen oxides, NO _x ^- is the waste water containing nitrogen oxides, in the presence of a specific porous carbon material catalyst, Exhaust gas containing nitrogen oxides or/and wastewater containing nitrogen oxides undergo an electrochemical reaction with α-keto acid compounds, and amino acids are obtained by electrolysis.

Specifically, the electrolytic cell can be a conventional electrolytic cell, such as a sealed three-electrode H-type electrolytic cell, a sealed two-electrode electrolytic cell, and a square electrolytic cell.

The method for producing amino acids in this application does not have high requirements on the concentration of the nitrogen source. From the test results, it can be seen that amino acids can be produced even if the concentration of nitrogen oxides in waste gas containing nitrogen oxides or/and wastewater containing nitrogen oxides is 50mM, which can be achieved Millimolar nitrogen oxide conversion targets amino acids.

The method for producing amino acids in this application has no pressure requirements and can be carried out at one atmospheric pressure.

Specifically, the amino acids synthesized in this application exist in the electrolyte, and the electrolyte can be collected and purified through chromatography columns to obtain the amino acids.

In another embodiment, the exhaust gas containing nitrogen oxides includes one or more of NO, NO ₂ and N ₂ O; the waste water containing nitrogen oxides includes ammonia nitrogen, nitrate nitrogen and nitrite nitrogen. one or more of them.

The exhaust gas containing nitrogen oxides in this application can be industrial exhaust gas containing NO, NO ₂ and N ₂ O, rocket plane automobile exhaust, nitric acid factory exhaust, thermal power plant exhaust, gas generated by the combustion of coal used in daily life, etc.; containing Nitrogen oxide wastewater can be livestock farm wastewater, domestic wastewater, and nitric acid factory wastewater containing large amounts of ammonia nitrogen (NH ₃ or/and NH ₄ ⁺ ), nitrate nitrogen (NO ₃ ^- ), and nitrite nitrogen (NO ₂ ^- ). , Thermal power plant exhaust gas and wastewater, etc.

Specifically, when the catalyst, exhaust gas containing nitrogen oxides, and wastewater containing nitrogen oxides are sufficient, the electrocatalysis of the synthesis method of the present application can be continued without time limit.

It should be noted that the present application found that the porous carbon material catalyst has the function of electrocatalyzing the synthesis of amino acids. The porous carbon material catalyst required for the amino acid synthesis method provided by the present application can be an existing commercially available conventional porous carbon material catalyst, and can be a co-catalyst. Valent organic framework materials, metal-organic framework materials, nitrogen-containing metal-organic framework materials and other materials can also be porous carbon skeletons loaded with heteroatoms or/and multi-metal atoms. The porous carbon material catalysts are further limited and explained below. .

The porous carbon material catalyst includes a porous carbon skeleton material and heteroatoms or/and multi-metal atoms distributed in the porous carbon skeleton; the porous carbon skeleton is mainly composed of microporous, mesoporous or macroporous carbon structural materials, The heteroatom is selected from one or more of N, O, S and P, and the multi-element metal atom is selected from Al, Cu, Mn, Co, Ni, Mg, Fe, Zn, Pt, Pd, Ag, One or more of Au and Ru

The nitrogen-containing metal-organic framework material is sintered under a protective atmosphere to obtain a porous carbon material catalyst; wherein the nitrogen-containing metal-organic framework material is selected from MET-6, ZIF-8, ZIF-67, MOF-74, PPy One or more of @MOF, PDA@MOF, HKUST-1, PCN series, MIL series, UiO series, UCM series.

In another embodiment, before sintering, the method further includes: mixing nitrogen-containing metal-organic framework materials, metal salts and organic solvents, filtering to obtain a solid, and removing the organic solvent of the solid to obtain M@MOF; @MOF is sintered in a protective atmosphere to obtain a porous carbon material catalyst doped with metal elements;

The metal salt is selected from the group consisting of soluble Al2+ salt, soluble Cu2 ⁺ salt, soluble Mn2 ⁺ salt, soluble Co2 ⁺ salt, soluble Ni2 ⁺ salt, soluble Pt2 ⁺ salt, soluble Mg2 ⁺ salt, and soluble Fe2 ⁺ one or more salts;

The organic solvent is selected from one or more of ethanol, methanol, water, N,N-dimethylformamide and acetone.

In another embodiment, the metal salt is selected from the group consisting of Al ²⁺ chloride, Al ²⁺ nitrate, Al ²⁺ acetate, Cu ²⁺ chloride, Cu ²⁺ nitrate, Acetate of Cu ²⁺ , chloride of Mn ²⁺ , nitrate of Mn ²⁺ , acetate of Mn ²⁺ , chloride of Co ²⁺ , nitrate of Co ²⁺ , nitrate of Co ²⁺ Acetate, Ni ²⁺ chloride, Ni ²⁺ nitrate, Ni ²⁺ acetate, Pt ²⁺ chloride, Pt ²⁺ nitrate, Pt ²⁺ acetate, One of Mg ²⁺ chloride, Mg ²⁺ nitrate, Mg ²⁺ acetate, Fe ²⁺ chloride, Fe ²⁺ nitrate and Fe ²⁺ acetate or Various.

Specifically, mix soluble zinc salt, auxiliary agent and amide compound to obtain a mixture; mix the mixture with 1H-1,2,3-triazole ligand to obtain MET-6; mix the MET-6, The metal salt and the solvent are mixed and filtered to obtain a solid. The solid is dried to obtain M@MOF; the M@MOF is calcined in a protective atmosphere to obtain a porous carbon material catalyst doped with metal atoms.

Specifically, the Fe@MET-6 precursor metal-organic framework was calcined under a protective atmosphere to obtain an iron-doped porous carbon material catalyst.

Specifically, the Cu@MET-6 precursor metal-organic framework was calcined in a protective atmosphere to obtain a copper-doped porous carbon material catalyst.

Specifically, the Cu-Fe@MET-6 precursor metal-organic framework is calcined in a protective atmosphere to obtain a copper-iron doped porous carbon material catalyst.

Specifically, the Ni@MET-6 precursor metal-organic framework was calcined in a protective atmosphere to obtain a nickel-doped porous carbon material catalyst.

Specifically, the Ni-Pt@MET-6 precursor metal-organic framework was calcined in a protective atmosphere to obtain a nickel-platinum doped porous carbon material catalyst.

Specifically, the Fe-Al@MET-6 precursor metal-organic framework was calcined in a protective atmosphere to obtain an iron-aluminum doped porous carbon material catalyst.

In another embodiment, the calcination temperature is 700°C ~ 1500°C; the calcination time is 2h ~ 8 h.

The purpose of this application is to address the problems of high energy consumption and easy secondary pollution in the treatment of nitrogen oxide exhaust gas and wastewater in the prior art. This application provides a method for producing amino acids from nitrogen oxide exhaust gas and wastewater, using nitrogen in the exhaust gas and wastewater. Oxides or nitrate ions are used as nitrogen sources, and α-keto acid compounds are used as carbon sources. Under the action of specific catalysts, nitrogen oxides in exhaust gas and wastewater are converted into amino acids through green and environmentally friendly electrochemical methods to realize the utilization of exhaust gas and wastewater. The application of converting nitrogen oxides into amino acids has the advantages of economy, environmental protection, and no secondary pollution. At the same time, this application converts waste gas and wastewater into economically beneficial amino acids, which can achieve secondary value-added.

The technical problem to be solved by the present invention is also to provide a method for synthesizing amino acids. The method provided by the present invention can synthesize a variety of amino acids, and the synthesized amino acids have high purity and low reaction cost.

The invention provides a method for synthesizing amino acids, which includes the following steps:

Under the action of a catalyst, α-keto acids are used as amino acid precursors and nitrogen oxides are used as nitrogen sources to synthesize amino acids through electrocatalysis; the catalyst includes porous carbon self-supporting materials and a self-supporting material loaded on the porous carbon. Material on metal.

Specifically, the present invention uses the catalyst as the working electrode, uses the silver/silver chloride electrode as the reference electrode, uses the platinum electrode as the counter electrode, uses the amino acid precursor and the nitrogen source as the electrolyte, and performs an electrocatalytic reaction to obtain Amino acids.

In some embodiments of the present invention, the catalyst is used as the working electrode, the silver/silver chloride electrode is used as the reference electrode, the platinum electrode is used as the counter electrode, and the electrolyte solution, amino acid precursor and nitrogen source are used as the electrolyte , perform an electrocatalytic reaction to obtain amino acids; the electrolyte solution is selected from at least one of hydrochloric acid or potassium hydroxide; the concentration of the electrolyte solution is 0.1 mol/L to 0.5 mol/L.

In one embodiment, in an electrolytic cell provided with an anode chamber and a cathode chamber, the catalyst is used as a working electrode, and a silver/silver chloride electrode is used as a reference electrode. The working electrode and the reference electrode are in the In the cathode chamber; a platinum electrode is used as the counter electrode, and the counter electrode is in the anode chamber; the cathode chamber electrolyte is added to the cathode chamber, and the anode chamber electrolyte is added to the anode chamber to perform electrocatalytic reaction. , obtain amino acids; the cathode chamber electrolyte includes an electrolyte solution, an amino acid precursor and a nitrogen source, the anode chamber electrolyte includes an electrolyte solution, the electrolyte solution in the cathode chamber electrolyte and the anode chamber electrolyte. The electrolyte solution is the same; the electrolyte solution is selected from at least one of hydrochloric acid or potassium hydroxide; the concentration of the electrolyte solution is 0.1 mol/L to 0.5 mol/L.

The catalyst of the present invention includes a porous carbon self-supporting material and a metal supported on the porous carbon self-supporting material. The inventor of the present application creatively discovered that the catalyst can electrocatalytically convert harmful nitrogen oxides into high-value amino acids required for life, while also achieving effective management of nitrogen oxides and turning waste into treasure. The porous carbon self-supporting material of the present invention has self-supporting characteristics, does not require an external binder, and avoids weak adsorption connection between the catalyst and the base electrode; at the same time, it has good mechanical strength and flexibility, and can be easily customized into specific sizes and thickness, low cost, easy to scale up and prepare, and has potential industrial application prospects. In some embodiments of the present invention, the pore volume of the porous carbon self-supporting material is 0.01cm ³ g ^-1 ~ 10.0cm ³ g ^-1 ; the pore size of the porous carbon self-supporting material is 0.5nm ~ 100nm; the specific surface area of the porous carbon self-supporting material is 10m ² g ^-1 ~ 3000m ² g ^-1 . In certain embodiments of the invention, the porous carbon self-supporting material is selected from carbon fiber membranes.

The porous carbon self-supporting material in the catalyst of the present invention has abundant metal sites, and the metal sites are evenly distributed on the porous interconnected porous carbon self-supporting material, which provides a safe space for the diffusion of nitrogen oxides and electron transmission. Important channels; the metal and porous carbon self-supporting materials in the catalyst of the present invention can be flexibly combined and matched, and are cheap and easy to obtain. In some embodiments of the invention, the metal supported on the porous carbon self-supporting material is selected from the group consisting of manganese, iron, cobalt, nickel, copper, zinc, titanium, vanadium, chromium, molybdenum, ruthenium, rhodium, palladium, At least one of platinum and silver.

The catalyst of the present invention also includes a non-metal element doped in the porous carbon self-supporting material; the non-metal element is selected from at least one of N, O, F, B, P, and S. In some embodiments of the present invention, the catalyst includes CoFe alloy-supported N-doped carbon fiber membrane, NiFe alloy-supported N-doped carbon fiber membrane, Fe-supported N-doped carbon fiber membrane, Co-supported N-doped carbon fiber membrane, Ni-loaded N-doped carbon fiber membrane, Mn-loaded N-doped carbon fiber membrane, Cu-loaded N-doped carbon fiber membrane, Zn-loaded N-doped carbon fiber membrane, Ti-loaded N-doped carbon fiber membrane, V-loaded N-doped carbon fiber membrane, Cr-loaded N-doped carbon fiber membrane, Mo-loaded N-doped carbon fiber membrane, Ru-loaded N-doped carbon fiber membrane, Rh-loaded N-doped carbon fiber membrane, Pd-loaded N-doped carbon fiber membrane , at least one of Pt-loaded N-doped carbon fiber membrane and Ag-loaded N-doped carbon fiber membrane.

In the present invention, α-keto acid compounds are used as amino acid precursors. In certain embodiments of the invention, the α-keto acid compound is selected from the group consisting of pyruvate, 4-hydroxyphenylpyruvate, 3-hydroxypyruvate, 3-thiopyruvate, and 3-methyl-2 -Oxybutyric acid, 3-indolepyruvate, imidazole-4-pyruvate, 6-amino-2-oxohexanoic acid, 4-(methylthio)-2-oxo-butyric acid, 3-hydroxy- 2-oxo-butyric acid, 4-amino-2,4-dioxobutyric acid, 5-amino-2,5-dioxopentanoic acid, δ-guanidino-α-ketovaleric acid, 3- Methyl-2-oxyvaleric acid, 3-methyl-2-oxybutyric acid, 4-methyl-2-oxopentanoic acid, phenylpyruvic acid, glyoxylic acid, oxaloacetic acid, α-ketoglutaric acid of acid, 2-butyronic acid, 2-pentanonic acid, 2-oxohexanoic acid, 2-cyclobutyl-2-carbonylacetic acid, 2-oxy-4-phenylbutyric acid and benzoylformic acid At least one. In some embodiments, the concentration of the amino acid precursor is 5mmol/L～10mol/L, preferably 5mmol/L～5mol/L, more preferably 5mmol/L～0.5mol/L, more preferably 5mmol/L L to 0.1 mol/L, more preferably 5 mmol/L to 0.05 mol/L.

The present invention uses nitrogen oxides as the nitrogen source, catalyzes the reduction of the nitrogen oxides to form hydroxylamine NH ₂ OH through electrochemical catalytic reactions, and is coupled with α-keto acid compounds such as α-keto acids and then reduced and hydrogenated to form α-keto acids. Amino acids; the present invention can also directly use NH ₂ OH or NH ₃ as nitrogen oxides to carry out the above reaction to form α-amino acids. In practical applications, the present invention can use automobile exhaust gas (taking nitric oxide in nitrogen oxides as an example) or wastewater (taking nitrate and nitrite as examples) as nitrogen sources. In some embodiments of the present invention, the nitrogen oxide is selected from at least one of NO, NO ₂ , NO ₂ ^- , NO ₃ ^- , N ₂ O, NH ₂ OH, and NH ₃ .

The nitrogen source of the present invention can participate in the electrocatalytic synthesis of amino acids in the form of gas or liquid. In some embodiments of the present invention, the nitrogen source is gas, and the flow rate of the nitrogen source is above 5 mL/min. In one embodiment, the flow rate of the nitrogen source is 10 mL/min to 15 mL/min. in the present invention In some embodiments, the nitrogen source is liquid, and the concentration of the nitrogen source is 5mmol/L~2000mmol/L, preferably 5mmol/L~1000mmol/L, more preferably 5mmol/L~500mmol/L, and more More preferably, it is 5 mmol/L to 100 mmol/L, and still more preferably, it is 5 mmol/L to 50 mmol/L.

In the present invention, under the action of the above catalyst, the above amino acid precursor and the nitrogen source are electrocatalytically reacted to synthesize the amino acid. In some embodiments of the present invention, the voltage of the electrocatalysis is -5V vs. RHE or above. In one embodiment, the voltage of the electrocatalysis is -3V vs. RHE ~ -0.5V vs. RHE. In one embodiment, the voltage of the electrocatalysis is -2V vs. RHE ~ -0.7V vs. RHE. In one embodiment, the voltage of the electrocatalysis is -1.1V vs. RHE ~ -0.9V vs. RHE.

Under the action of the above catalyst, the present invention has well achieved high catalytic activity, high selectivity, high yield and ultra-long cycle stability for the electrosynthesis of amino acids from nitrogen oxides; through the method of the present invention, it is possible to artificially synthesize up to 13 kinds of amino acids, covering three categories: essential amino acids for human body, non-essential amino acids for human body and amino acids not involved in protein synthesis, and have wide universal applicability. In certain embodiments of the invention, the amino acid is leucine, isoleucine, valine, alanine, glutamic acid, aspartic acid, glycine, 2-aminobutyric acid, 2- At least one of aminovaleric acid, 2-aminocaproic acid, 2-amino-cyclobutylacetic acid, homophenylalanine, and phenylglycine.

The invention also provides a method for preparing the above-mentioned catalyst, which includes: loading a metal source on a porous carbon self-supporting material to obtain the above-mentioned catalyst; the method for preparing the porous carbon self-supporting material includes electrospinning, gel blade coating or Gel spin coating method.

In some embodiments of the present invention, the porous carbon self-supporting material in the above catalyst is a carbon fiber membrane. The preparation method of the above catalyst includes: mixing a metal source and a high molecular carbon-containing polymer, performing electrospinning, and electrospinning The product obtained after silking is subjected to heat treatment to obtain the above catalyst. Specifically, the preparation method of the above-mentioned catalyst includes: mixing a metal source and a high molecular carbon-containing polymer to obtain an electrospinning solution, followed by electrospinning, and heat-treating the electrospinning product to obtain the above-mentioned catalyst. In some embodiments, the preparation method of the above-mentioned catalyst includes: mixing a metal source and a high molecular carbon-containing polymer to obtain an electrospinning solution, then performing electrospinning, and pre-oxidizing the product obtained after electrospinning, and then performing Calcined to obtain the above catalyst.

In one embodiment, the metal source is selected from metal organic frameworks, metal salts or MOF composite materials; the MOF composite material is loaded with metal salts or metal particles; the metal is selected from manganese, iron, cobalt, nickel, copper , at least one of zinc, titanium, vanadium, chromium, molybdenum, ruthenium, rhodium, palladium, platinum and silver. In one embodiment, the high molecular carbon-containing polymer is selected from at least one selected from the group consisting of polyacrylonitrile, polyvinylidene fluoride, and polylactic acid. In one embodiment, the temperature of the pre-oxidation treatment is 600°C-400°C; the time of the pre-oxidation treatment is 1h-24h; the temperature of the calcination is 400°C-1200°C; the calcination time is 1h～24h.

The above metal source can also be a metal source compounded with non-metal elements. The prepared catalyst includes a porous carbon self-supporting material, a metal loaded on the porous carbon self-supporting material, and a metal doped in the porous carbon self-supporting material. non-metallic elements in. In some embodiments of the present invention, the preparation method of the metal source compounded with non-metal elements includes: mixing the metal source, sodium citrate dihydrate and the non-metal source, and then In response, a metal source compounded with non-metal elements is obtained. Specifically, the preparation method of the metal source compounded with non-metal elements includes: mixing the metal source and sodium citrate dihydrate to obtain a mixed solution, adding the non-metal source solution into the mixed solution, and stirring for 5 to 15 minutes. Let the reaction stand for 6 to 30 hours to obtain a metal source compounded with non-metal elements. In one embodiment, the non-metal source is selected from at least one of N source, O source, F source, B source, P source and S source. The metal source is the same as above and will not be described again. In one embodiment, the non-metal source is selected from N sources, the N source is selected from potassium ferricyanate, and the preparation method of the metal source compounded with non-metal elements includes: combining the metal source and citric acid dihydrate Mix sodium to obtain a mixed solution, add potassium ferricyanate into the mixed solution, stir for 5 to 15 minutes, and then allow to react for 6 to 30 hours to obtain a metal source complex nitrogen-doped Prussian blue analogue (PBA).

The invention provides a method for synthesizing amino acids, which includes the following steps: under the action of a catalyst, α-keto acid compounds are used as amino acid precursors, nitrogen oxides are used as nitrogen sources, and amino acids are synthesized through electrocatalysis; the catalyst includes a porous A carbon self-supporting material and a metal supported on the porous carbon self-supporting material. The method provided by the invention can synthesize a variety of amino acids, and the synthesized amino acids have high purity and low reaction cost. Experiments have shown that the method of the present invention has successfully achieved the synthesis of amino acids such as leucine. The output reaches gram level (1.30g) within 24 hours and has long-term cycle stability. It can be seen from the nuclear magnetic spectrum that the purity of the synthesized amino acids is high. , the purity after further simple purification can be as high as 92%.

The present application provides an amino acid synthesis device, which is used to solve the defects of high energy consumption, long time consumption, and complicated product separation and purification existing in the existing methods of synthesizing amino acids.

In view of this, the present application provides an amino acid synthesis device, which includes:

Electrolysis reaction tanks and product handling systems;

The electrolysis reaction tank includes a stirring tank, a positive electrode plate, a negative electrode plate, an external circuit, a liquid feed port, a gas feed port and a product discharge port;

The outer wall of the stirring tank is respectively provided with a liquid feed port, a gas feed port and a product discharge port;

The positive electrode plate and the negative electrode plate are respectively arranged inside the stirring tank; the external circuit is arranged outside the stirring tank, and the external circuit is connected to the positive electrode plate and the negative electrode respectively. The electrode plates are connected, the surface of the positive electrode plate is coated with a commercial metal carbon catalyst; the surface of the negative electrode plate is coated with a catalyst for electrocatalytic synthesis of amino acids;

The product treatment system includes a centrifuge, an extraction machine and a distillation machine; the centrifuge is connected to the extraction machine, the centrifuge is connected to the distillation machine, the extraction machine is connected to the distillation machine; the The product discharge port is respectively connected with the inlet of the centrifuge, the inlet of the extraction machine and the inlet of the distillation machine; the first outlet of the centrifuge, the first outlet of the extraction machine and the distillation machine The first outlets are interconnected to form a product outlet of the product processing system.

In another embodiment, the synthesis device of the present application further includes a liquid material filter and a liquid material detector. The outlet of the liquid material filter is connected to the inlet of the liquid material detector. The outlet of the liquid material detector Connected to the liquid feed port.

In another embodiment, the synthesis device of the present application also includes a gas filter, a gas concentrator and a gas detector, the gas filter, the gas concentrator and the gas detector are connected in sequence, the The outlet of the gas detector is connected with the gas feed port.

In another embodiment, the electrolysis reaction tank further includes: a sampling port, a monitoring sensor and a detector;

A sampling port is provided on the outer wall of the stirring tank, the monitoring sensor is arranged inside the stirring tank, and the detector is connected to the liquid in the stirring tank through the sampling port.

In another embodiment, the synthesis device of the present application further includes a temporary storage tank. The second outlet of the centrifuge, the second outlet of the extraction machine and the second outlet of the distillation machine are respectively connected with the temporary storage tank. The inlet is connected, and the outlet of the temporary storage tank is connected with the liquid feed port of the stirring tank.

In another embodiment, the synthesis device of the present application further includes a waste treatment system. The third outlet of the centrifuge, the third outlet of the extraction machine and the third outlet of the distillation machine are respectively connected with the waste treatment system. connect.

In another embodiment, the synthesis device of the present application also includes a control system, which is connected to the stirring tank, the external circuit, the liquid feed port, the gas feed port, and the product outlet respectively. The material port, the centrifuge, the extraction machine and the distillation machine are connected.

Specifically, the porous carbon material catalyst includes a porous carbon skeleton and heteroatoms or/and multi-metal atoms distributed in the porous carbon skeleton. The porous carbon skeleton mainly includes microporous, mesoporous and macroporous carbon structural materials. , the heteroatom is selected from one or more of N, O, S and P, and the multi-element metal atom is selected from Al, Cu, Mn, Co, Ni, Mg, Fe, Zn, Pt, Pd, Ag , one or more of Au and Ru.

Specifically, the preparation method of the porous carbon material catalyst includes:

The nitrogen-containing metal-organic framework material is calcined under a protective atmosphere to obtain a catalyst; wherein the nitrogen-containing metal-organic framework material is selected from MET-6, ZIF-8, ZIF-67, MOF-74, UiO-66, One or more of MIL-101, PPy@MOF, PDA@MOF, HKUST-1, PCN series, MIL series, UiO series and UCM series.

Specifically, before the calcination, the method further includes: mixing the nitrogen-containing metal-organic framework material, metal salt and solvent, filtering to obtain a solid, and drying the solid to obtain M@MOF;

The preparation method of the porous carbon material catalyst includes: calcining the M@MOF under a protective atmosphere to obtain a catalyst;

The metal salt is selected from the group consisting of Al ³⁺ chloride, Al ³⁺ nitrate, Al ³⁺ acetate, Al ³⁺ sulfate, Cu ²⁺ chloride, Cu ²⁺ nitrate , Cu ²⁺ acetate, Cu ²⁺ sulfate, Mn ²⁺ chloride, Mn ²⁺ nitrate, Mn ²⁺ acetate, Mn ²⁺ sulfate, Co ²⁺ Chloride, Co ²⁺ nitrate, Co ²⁺ acetate, Co ²⁺ sulfate, Ni ²⁺ chloride, Ni ²⁺ nitrate, Ni ²⁺ acetate, Ni ²⁺ sulfate, Mg ²⁺ chloride, Mg ²⁺ nitrate, Mg ²⁺ acetate, Mg ²⁺ sulfate ^, Fe ²⁺ chloride, Fe 2+ nitrate, Fe ²⁺ acetate, Fe ²⁺ sulfate, Fe ³⁺ chloride, Fe ³⁺ nitric acid Salt, Fe ³⁺ acetate, Fe ³⁺ sulfate, Zn ²⁺ chloride, Zn ²⁺ nitrate, Zn ²⁺ acetate, Zn ²⁺ sulfate, Zn ²⁺ Chloride salt of Zn ²⁺ , nitrate salt of Zn 2+, acetate salt of Zn ²⁺ , sulfate salt of Zn ²⁺ , chloride salt of Pt ²⁺ , nitrate salt of Pt ²⁺ , acetate salt of Pt ²⁺ , Pt ²⁺ chlorate, Pd ²⁺ chloride, Pd ²⁺ nitrate, Pd ²⁺ acetate, Pd ²⁺ chlorate, Ag ²⁺ chloride, Ag ²⁺ sulfate, Ag ²⁺ acetate, Ag ²⁺ sulfate, Au ³⁺ chloride, Au ³⁺ sulfate, Au ³⁺ acetate, Au ³⁺ chlorate, One or more of Ru ³⁺ chloride, Ru ²⁺ sulfate, Ru ³⁺ acetate and Ru ⁴⁺ chlorate;

The solvent is selected from one or more of ethanol, methanol, N,N-dimethylformamide, chloroform, distilled water and tetrahydrofuran.

Specifically, the calcination temperature is 600°C to 1500°C; the calcination time is 2h to 8h.

Specifically, the preparation method of MET-6 includes:

Step 2: Mix the mixture with 1H-1,2,3-triazole ligand to obtain MET-6.

Specifically, in step 1, the soluble zinc salt is selected from zinc chloride or/and zinc nitrate; the auxiliary agent is selected from one or more of ethanol, water and ammonia; the amide compound is selected from N , one or more of N-dimethylformamide, N,N-diethylformamide and N,N-dimethylacetamide.

Specifically, the preparation method of the catalyst includes: mixing soluble zinc salt, auxiliary agent and amide compound to obtain a mixture; mixing the mixture with 1H-1,2,3-triazole ligand to obtain MET-6 ; Mix the MET-6, metal salt and solvent, filter to obtain a solid, and dry the solid to obtain M@MOF; Calculate the M@MOF under a protective atmosphere to obtain doped heteroatoms and metal atoms. Porous carbon material catalyst.

Specifically, mix soluble zinc salt, auxiliary agent and amide compound to obtain a mixture; mix the mixture with 1H-1,2,3-triazole ligand to obtain MET-6; mix the MET-6 in Calculate under a protective atmosphere to obtain a catalyst for synthesizing amino acids, which is a porous carbon material catalyst doped with heteroatoms.

It can be seen from the above technical solutions that this application has the following advantages:

In this application, an amino acid synthesis device is provided. The liquid raw material is introduced into the stirring kettle from the liquid feed port, the gas raw material is introduced into the stirring kettle from the gas feed port, and the external circuit controls the positive electrode plate and the negative electrode plate to interact with the stirring kettle. Electrocatalytic voltage is applied to the materials inside, and the control voltage range is 0~5V; stirring tank The electric stirrer stirs the material while promoting full contact between the material and the catalyst on the electrode plate for electrocatalytic reaction. Under the action of the catalyst, α-keto acid compounds are used as carbon source raw materials, and nitrogen oxides are used as gaseous nitrogen source raw materials or/and Liquid nitrogen source raw material, after the catalyst and carbon source raw material nitrogen oxide are passed into the stirring kettle, the reactants containing amino acids are synthesized through electrocatalysis; the reactants from the stirring kettle are passed into the product treatment system, and the reactants are centrifuged, extracted and One or more operations in distillation to extract high-concentration and high-value amino acid products from the reactants, which are derived from the product outlet. Therefore, the synthesis device of the present application can be used to perform an electrocatalytic reaction using carbon source raw materials and nitrogen oxides to produce amino acids.

Description of the drawings

Figure 1 is a synthesis route diagram for synthesizing organic nitrogen-containing compounds according to the present invention;

Figure 2 is the NMR image of the acetone oxime product electrocatalytically synthesized by ZIF-8/PAN membrane;

Figure 3 shows the NMR image of the acetone oxime product electrocatalytically synthesized by commercial carbon cloth;

Figure 4 is the NMR image of the acetone oxime product electrocatalytically synthesized by CoFe-SSM membrane;

Figure 5 is the NMR image of the product electrocatalytically synthesized by ZIF-8/PAN membrane;

Figure 6 is the NMR image of the benzaldehyde oxime product electrocatalytically synthesized by ZIF-8/PAN membrane;

Figure 7 shows the NMR image of the product of benzylamine synthesized electrocatalytically by NO as a nitrogen source;

Figure 8 is the NMR image of the product of benzylamine electrocatalytically synthesized by NH ₂ OH as a nitrogen source;

Figure 9 is the NMR image of the product of furfurylamine synthesized electrocatalytically by NO as a nitrogen source;

Figure 10 is the NMR image of the product of isobutyronitrile synthesized by CoFe-SSM membrane electrocatalysis;

Figure 11 is the NMR image of the product of isobutyronitrile synthesized by electrocatalysis using commercial carbon cloth;

Figure 12 is the NMR image of the product of isobutyronitrile synthesized electrocatalytically by ZIF-8/PAN membrane;

Figure 13 is the NMR image of the product of electrocatalytic synthesis of isovaleronitrile using KNO ₂ as a nitrogen source;

Figure 14 is a schematic diagram of the synthesis route of amino acids provided by the present application;

Figure 15 is the H-NMR result of the valine standard sample provided in Example 16 of the present application;

Figure 16 is the LC-MS result after derivatization treatment of the valine standard sample provided in Example 16 of the present application;

Figure 17 is the H-NMR results of the electrolyte reacting for different times in the cathode chamber of Example 17 of the present application;

Figure 18 is the LC-MS result of the electrolyte in the cathode chamber provided in Example 17 of the present application;

Figure 19 is the H-NMR spectrum of the electrolyte in the cathode chamber under different electrolysis times and the corresponding peak area integration results provided in Example 17 of the present application;

Figure 20 is the conversion rate result of the raw material material (3-methyl-2-oxobutyric acid) for preparing valine in the cathode chamber under different electrolysis times provided in Example 17 of the present application;

Figure 21 is the H-NMR spectrum of valine prepared with different 3-methyl-2-oxobutyric acid concentrations and different NO gas flow rates provided in Example 18 of the present application and the corresponding peak area integration results;

Figure 22 is the H-NMR spectrum of valine prepared with different applied potentials provided in Example 19 of the present application and the corresponding peak area integration results;

Figure 23 is the H-NMR result of the electrolyte in the cathode chamber provided in Example 20 of the present application;

Figure 24 is the H-NMR result of the electrolyte in the cathode chamber provided in Example 21 of the present application;

Figure 25 is the H-NMR result of the electrolyte in the cathode chamber provided in Example 22 of the present application;

Figure 26 is the LC-MS result of the electrolyte in the cathode chamber provided in Example 22 of the present application;

Figure 27 is the LC-MS result of the electrolyte in the cathode chamber provided in Example 23 of the present application;

Figure 28 is the LC-MS result of the electrolyte in the cathode chamber provided in Example 24 of the present application;

Figure 29 is the H-NMR result of the electrolyte in the cathode chamber provided in Example 25 of the present application;

Figure 30 is the LC-MS result of the electrolyte in the cathode chamber provided in Example 25 of the present application;

Figure 31 is the H-NMR result of the electrolyte in the cathode chamber provided in Example 26 of the present application;

Figure 32 is the LC-MS result of the electrolyte in the cathode chamber provided in Example 26 of the present application;

Figure 33 is the LC-MS result of the electrolyte in the cathode chamber provided in Example 27 of the present application;

Figure 34 is the H-NMR result of the electrolyte in the cathode chamber provided in Example 28 of the present application;

Figure 35 is the LC-MS result of the electrolyte in the cathode chamber provided in Example 28 of the present application;

Figure 36 is the H-NMR result of the electrolyte in the cathode chamber provided in Example 29 of the present application;

Figure 37 is the LC-MS result of the electrolyte in the cathode chamber provided in Example 29 of the present application;

Figure 38 is the XRD pattern of CoFe-PBA precursor;

Figure 39 is the SEM image of CoFe-PBA precursor;

Figure 40 is the TEM image of CoFe-PBA precursor;

Figure 41 is the XRD pattern of CoFe/NC carbon fiber membrane;

Figure 42 is the SEM image of the CoFe/NC carbon fiber membrane;

Figure 43 is the TEM image of CoFe/NC carbon fiber membrane;

Figure 44 is the nitrogen adsorption and desorption curve of CoFe/NC carbon fiber membrane;

Figure 45 is the pore size distribution diagram of CoFe/NC carbon fiber membrane;

Figure 46 is the H-NMR spectrum of leucine synthesized after electrolysis for 6 hours using CoFe/NC carbon fiber membrane as a catalyst under the potential condition of -0.9V vs. RHE;

Figure 47 is a histogram of the selectivity of leucine after electrolysis for 6 hours using CoFe/NC carbon fiber membrane as a catalyst at different potentials;

Figure 48 is a histogram of the Faradaic efficiency and yield of leucine after electrolysis for 6 hours using CoFe/NC carbon fiber membrane as a catalyst at different potentials;

Figure 49 is a long cycle stability test chart of leucine synthesis using CoFe/NC carbon fiber membrane as a catalyst;

Figure 50 is the H-NMR spectrum of leucine synthesized after electrolysis for 6 hours using a CoFe/NC carbon fiber membrane as a catalyst and 15 mL/min NO ₂ gas as a nitrogen source under the potential condition of -0.7V vs. RHE. picture;

Figure 51 is the H-NMR spectrum of leucine synthesized after electrolysis for 6 hours using CoFe/NC carbon fiber membrane as catalyst and 100 mmol/L KNO ₂ as nitrogen source under the potential condition of -0.7V vs. RHE. ;

Figure 52 is the H-NMR spectrum of leucine synthesized after electrolysis for 3 hours using CoFe/NC carbon fiber membrane as catalyst and 1 mol/L KNO ₃ as nitrogen source under the potential condition of -1.1V vs. RHE. ;

Figure 53 shows electrolysis using FeFe/NC carbon fiber membrane as catalyst under the potential condition of -0.7V vs. RHE. H-NMR spectrum of leucine synthesized after 6 hours;

Figure 54 is the H-NMR spectrum of leucine synthesized after electrolysis for 6 hours using CoCo/NC carbon fiber membrane as a catalyst under the potential condition of -0.7V vs. RHE;

Figure 55 is the H-NMR spectrum of isoleucine synthesized after electrolysis for 6 hours under the potential condition of -0.7V vs. RHE;

Figure 56 is the H-NMR spectrum of valine synthesized after electrolysis for 6 hours under the potential conditions of -0.7V vs. RHE;

Figure 57 is the H-NMR spectrum of alanine synthesized after electrolysis for 6 hours under the potential condition of -0.7V vs. RHE;

Figure 58 is the H-NMR spectrum of glutamic acid synthesized after electrolysis for 6 hours under the potential condition of -0.7V vs. RHE;

Figure 59 is the H-NMR spectrum of aspartic acid synthesized after electrolysis for 6 hours under the potential condition of -0.7V vs. RHE;

Figure 60 is the H-NMR spectrum of glycine synthesized after electrolysis for 6 hours under the potential condition of -0.7V vs. RHE;

Figure 61 is the H-NMR spectrum of 2-aminobutyric acid synthesized after electrolysis for 6 hours under the potential condition of -0.7V vs. RHE;

Figure 62 is the H-NMR spectrum of 2-aminovaleric acid synthesized after electrolysis for 6 hours under the potential condition of -0.7V vs. RHE;

Figure 63 is the H-NMR spectrum of 2-aminocaproic acid synthesized after electrolysis for 6 hours under the potential condition of -0.7V vs. RHE;

Figure 64 is the H-NMR spectrum of 2-amino-cyclobutylacetic acid synthesized after electrolysis for 6 hours under the potential condition of -0.7V vs. RHE;

Figure 65 is the H-NMR spectrum of homophenylalanine synthesized after electrolysis for 6 hours under the potential condition of -0.9V vs. RHE;

Figure 66 is the H-NMR spectrum of phenylglycine synthesized after electrolysis for 6 hours under the potential condition of -0.9V vs. RHE;

Figure 67 is a photo of the purified leucine synthesized after continuous electrolysis for 24 hours under the potential condition of -0.9V vs. RHE;

Figure 68 is the H-NMR spectrum of the purified leucine synthesized after continuous electrolysis for 24 hours under the potential condition of -0.9V vs. RHE;

Figure 69 is the H-NMR spectrum of leucine synthesized after CoFe alloy was directly dropped on the glassy carbon electrode as a catalyst and electrolyzed for 6 hours under the potential condition of -0.7V vs. RHE;

Figure 70 is a schematic structural diagram of the first amino acid synthesis device in the embodiment of the present application;

Figure 71 is a schematic structural diagram of the second amino acid synthesis device in the embodiment of the present application.

Detailed ways

The invention discloses a synthesis method and a synthesis device of organic nitrogen-containing compounds. Those skilled in the art can learn from the contents of this article and appropriately improve the implementation of process parameters. It should be noted that all similar substitutions and modifications are obvious to those skilled in the art, and they are deemed to be included in the present invention. The methods and applications of the present invention have been described through preferred embodiments. Relevant persons can obviously modify or appropriately change and combine the methods and applications herein without departing from the content, spirit and scope of the present invention to implement and apply the present invention. Invent technology.

Example 1

The CoFe-SSM membrane catalyst is synthesized according to the following steps:

1. Synthesis of CoFe-PBA precursor: Dissolve a certain amount of CoCl ₂ ·6H ₂ O and a certain amount of sodium citrate dihydrate in 500 mL of deionized water to obtain liquid A; uniformly dissolve a certain amount of potassium ferricyanate. Dissolve in 500 mL deionized water to obtain liquid B; under magnetic stirring, quickly introduce liquid B into liquid A, stir for 10 minutes and let stand for 24 hours, then centrifuge the obtained product, and wash with water and ethanol. Three times, continue centrifugation to obtain the CoFe-PBA precursor.

2. Preparation of CoFe-PBA/PAN membrane: Mix the above-synthesized CoFe-PBA precursor with polyacrylonitrile (PAN) and N,N-dimethylformamide (DMF) and stir evenly to obtain an electrospinning solution. The electrospinning solution is subjected to an electrospinning process to prepare a CoFe-PBA/PAN membrane.

3. Preparation of CoFe-SSM membrane: The CoFe-PBA/PAN membrane obtained above is first pre-oxidized in air, and then calcined at high temperature under an argon atmosphere to obtain a CoFe/NC carbon fiber membrane (i.e., CoFe-SSM membrane).

Example 2

ZIF-8/PAN membrane catalyst is synthesized according to the following steps:

1. Synthesis of ZIF-8 precursor: Add a certain amount of Zn(NO ₃ ) ₂ ·6H ₂ O and a certain amount of 2-methylimidazole to 1000 mL of methanol. Stir for 24 hours under magnetic stirring, then centrifuge the resulting product, wash it three times with water and ethanol, and centrifuge to obtain the ZIF-8 precursor.

2. Preparation of ZIF-8/PAN membrane: Mix the above-synthesized ZIF-8 precursor with polyacrylonitrile (PAN) and N,N-dimethylformamide (DMF) and stir evenly to obtain an electrospinning solution. The electrospinning solution is subjected to an electrospinning process to prepare a ZIF-8/PAN membrane.

3. Preparation of ZIF-8/PAN membrane: The ZIF-8/PAN membrane obtained above is first pre-oxidized in air, and then calcined at high temperature in an argon atmosphere to obtain a ZIF-8/PAN carbon fiber membrane.

Example 3

The synthesis method of organic nitrogen-containing compounds disclosed in the present invention is shown in Figure 1. Figure 1 is a synthesis route diagram for the synthesis of organic nitrogen-containing compounds in the present invention. As can be seen from Figure 1, in the present invention, nitrogen oxides are first electrically reduced to form NH. ₃ or NH ₂ OH, and then used as a nucleophile to attack the carbonyl group to obtain intermediates such as imines or oximes, which are subsequently reduced and hydrogenated to form amines. If decarboxylated or oxidatively dehydrated, nitriles can be obtained.

Preparation of oxime is carried out in a sealed three-electrode H-type electrolytic cell with the method of the present invention:

In this embodiment, under the action of a ZIF-8/PAN membrane catalyst, acetone is used as the carbon source and NO is used as the nitrogen source to synthesize acetone oxime through electrocatalysis.

First, a self-made ZIF-8/PAN membrane was obtained by electrospinning and calcination, and the resulting ZIF-8/PAN membrane was clamped on a platinum electrode clip as a working electrode; a saturated silver/silver chloride electrode was used As a reference electrode; the working electrode and the reference electrode are placed in the cathode chamber of the H-type electrolytic cell; a platinum piece is used as the counter electrode and placed in the anode chamber of the H-type electrolytic cell. Add 31 mL of cathode chamber electrolyte to the cathode chamber, which is an aqueous solution (containing 0.1 mol/L KOH and 10 mmol/L acetone); and add 30 mL of anode chamber electrolyte to the anode chamber, so The anode chamber electrolyte is a 0.1 mol/L KOH aqueous solution. Before performing electrocatalysis, first use high-purity argon gas to ventilate the sealed cathode electrolytic chamber for 6 minutes to replace all oxygen and air in the solution and above the electrolytic cell with inert argon gas, and then use NO to ventilate the sealed cathode. Ventilate the electrolysis chamber for 6 minutes. During the electrocatalysis process, the NO gas flow is controlled at about 15 sccm, and electrolysis is performed using a constant voltage method. The voltage is set to -1.1V vs. RHE. After 1 hour of electrolysis, the electrolyte in the cathode chamber is collected for product identification. Qualitative analysis is carried out through hydrogen nuclear magnetic resonance spectroscopy (H-NMR). In H-NMR, the spectrum of H atoms on acetone oxime is used as the basis for judgment. The results are shown in Figure 2. Figure 2 shows the electrocatalytic synthesis of acetone oxime products. NMR chart, the abscissa in Figure 2 is f1 (ppm). It can be seen from the results of H-NMR that acetone oxime can be successfully synthesized; the yield is 41.6%, the Faradaic efficiency is 4.11%, and the selectivity is 94.6%.

Example 4

In this embodiment, acetone is used as the carbon source and NO as the nitrogen source under the action of a commercial carbon cloth catalyst, and acetone oxime is synthesized through electrocatalysis.

First, a piece of commercial carbon cloth with an area of 3cm×2cm is clamped on the platinum electrode clip as the working electrode; a saturated silver/silver chloride electrode is used as the reference electrode; the working electrode and the reference electrode are placed In the cathode compartment of an H-type electrolytic cell. A platinum piece was used as the counter electrode and placed in the anode chamber of the H-type electrolytic cell. Add 31 mL of cathode chamber electrolyte, which is an aqueous solution (containing 0.1 mol/L KOH and 10 mmol/L acetone), into the cathode chamber; and add 30 mL of 0.1 mol/L KOH solution into the anode chamber. as electrolyte. Before electrocatalysis, high-purity argon gas is used to ventilate the sealed cathode electrolytic chamber for 6 minutes to replace all oxygen and air in the solution and above the electrolytic cell with inert argon gas. Then use NO to ventilate the sealed cathode electrolytic chamber for 6 minutes. During the electrocatalysis process, the NO gas flow was controlled at about 15 sccm, and electrolysis was performed using a constant voltage method. The voltage was set to -1.1V vs. RHE. After 3 hours of electrolysis, the electrolyte in the cathode chamber was collected for product identification. Qualitative analysis was performed by hydrogen nuclear magnetic resonance spectroscopy (H-NMR). In H-NMR, the spectrum of H atoms on acetone oxime is used as the basis for judgment. The results are shown in Figure 3. Figure 3 is the NMR image of the acetone oxime product electrocatalytically synthesized by commercial carbon cloth. The abscissa in Figure 3 is f1 ( ppm). It can be seen from the results of H-NMR that acetone oxime can be successfully synthesized with a yield of 20.3%, a Faradaic efficiency of 5.59%, and a selectivity of 83.8%.

Example 5

In this embodiment, acetone is used as the carbon source and NO as the nitrogen source under the catalyst of the CoFe-SSM membrane to synthesize acetone oxime through electrocatalysis.

First, a self-made CoFe-SSM membrane obtained by electrospinning and calcination is clamped on a platinum electrode clip as a working electrode; a saturated silver/silver chloride electrode is used as a reference electrode; the working electrode and reference electrode Placed in the cathode chamber of the H-type electrolytic cell. A platinum piece was used as the counter electrode and placed in the anode chamber of the H-type electrolytic cell. Add 31 mL of cathode chamber electrolyte, which is an aqueous solution (containing 0.1 mol/L KOH and 10 mmol/L acetone), into the cathode chamber; and add 30 mL of 0.1 mol/L KOH solution into the anode chamber. as electrolyte. Before electrocatalysis, high-purity argon gas is used to ventilate the sealed cathode electrolytic chamber for 6 minutes to replace all oxygen and air in the solution and above the electrolytic cell with inert argon gas. Then use NO to ventilate the sealed cathode electrolytic chamber for 6 minutes. During the electrocatalysis process, the NO gas flow was controlled at about 15 sccm, and electrolysis was performed using a constant voltage method. The voltage was set to -1.1V vs. RHE. After 6 hours of electrolysis, the electrolyte in the cathode chamber was collected for product identification. Qualitative analysis was performed by hydrogen nuclear magnetic resonance spectroscopy (H-NMR). In H-NMR, the spectrum of H atoms on acetone oxime is used as the basis for judgment. The results are shown in Figure 4. Figure 4 is the NMR image of the acetone oxime product electrocatalytically synthesized by CoFe-SSM membrane. The abscissa in Figure 4 is f1 (ppm). It can be seen from the results of H-NMR that acetone oxime can be successfully synthesized with a yield of 9.89%, a Faradaic efficiency of 5.18%, and a selectivity of 90.6%.

Example 6

In this example, under the action of ZIF-8/PAN membrane (ZIF-8/PAN membrane) catalyst, butanone is used as the carbon source and NO is used as the nitrogen source to synthesize butanone oxime through electrocatalysis.

First, the self-made ZIF-8/PAN membrane obtained by electrospinning and calcination was clamped on a platinum electrode clip as a working electrode; a saturated silver/silver chloride electrode was used as a reference electrode; the working electrode and reference The specific electrode is placed in the cathode chamber of the H-type electrolytic cell. A platinum piece was used as the counter electrode and placed in the anode chamber of the H-type electrolytic cell. Add 31 mL of cathode chamber electrolyte, which is an aqueous solution (containing 0.1 mol/L KOH and 3.3 mmol/L butanone), into the cathode chamber, and add 30 mL of 0.1 mol/L ethyl ketone into the anode chamber. KOH solution serves as electrolyte. Before electrocatalysis, high-purity argon gas is used to ventilate the sealed cathode electrolytic chamber for 6 minutes to replace all oxygen and air in the solution and above the electrolytic cell with inert argon gas. Then use NO to ventilate the sealed cathode electrolytic chamber for 6 minutes. During the electrocatalysis process, the NO gas flow is controlled at about 15 sccm, and electrolysis is performed using a constant voltage method. The voltage is set to -1.1V vs. RHE. After 1 hour of electrolysis, the electrolyte in the cathode chamber is collected for product identification. Qualitative analysis was performed by hydrogen nuclear magnetic resonance spectroscopy (H-NMR). In H-NMR, the spectrum of H atoms on butanone oxime is used as the basis for judgment. The results are shown in Figure 5. Figure 5 is the NMR image of the product electrocatalytically synthesized by ZIF-8/PAN membrane. Figure 5 The abscissa is f1 (ppm). From the H-NMR results, it can be seen that butanone oxime can be successfully synthesized with a yield of 53.3%, a Faradaic efficiency of 9.61%, and a selectivity of 61.1%.

Example 7

In this example, under the action of ZIF-8/PAN membrane (ZIF-8/PAN membrane) catalyst, benzaldehyde is used as the carbon source and NO is used as the nitrogen source to synthesize benzaldehyde oxime through electrocatalysis.

First, the self-made ZIF-8/PAN membrane obtained by electrospinning and calcination was clamped on a platinum electrode clip. as the working electrode; a saturated silver/silver chloride electrode as the reference electrode; the working electrode and the reference electrode are placed in the cathode chamber of the H-type electrolytic cell. A platinum piece was used as the counter electrode and placed in the anode chamber of the H-type electrolytic cell. Add 31 mL of cathode chamber electrolyte, which is an aqueous solution (containing 0.1 mol/L KOH and 10 mmol/L benzaldehyde), into the cathode chamber, and add 30 mL of 0.1 mol/L KOH into the anode chamber. The solution acts as an electrolyte. Before electrocatalysis, high-purity argon gas is used to ventilate the sealed cathode electrolytic chamber for 6 minutes to replace all oxygen and air in the solution and above the electrolytic cell with inert argon gas. Then use NO to ventilate the sealed cathode electrolytic chamber for 6 minutes. During the electrocatalysis process, the NO gas flow was controlled at about 15 sccm, and electrolysis was performed using a constant voltage method. The voltage was set to -1.1V vs. RHE. After 1 hour of electrolysis, the electrolyte in the cathode chamber was collected for product identification. Qualitative analysis was performed by hydrogen nuclear magnetic resonance spectroscopy (H-NMR). In H-NMR, the spectrum of H atoms on benzaldehyde oxime is used as the basis for judgment. The results are shown in Figure 6. Figure 6 is the NMR image of the benzaldehyde oxime product electrocatalytically synthesized by ZIF-8/PAN membrane. Figure 6 The abscissa is f1 (ppm). It can be seen from the H-NMR results that benzaldehyde oxime can be successfully synthesized with a yield of 58.9%, a Faradaic efficiency of 20.11%, and a selectivity of 64.3%.

Example 8

The preparation of organic amines is carried out in a sealed three-electrode H-type electrolytic cell using the method of the present invention:

In this example, commercial carbon cloth is used as a catalyst, benzaldehyde is used as the carbon source, and NO is used as the nitrogen source to synthesize benzylamine through electrocatalysis.

First, clamp commercial carbon cloth on the platinum electrode clip as the working electrode; use the saturated silver/silver chloride electrode as the reference electrode; place the working electrode and reference electrode in the H-type electrolytic cell cathode chamber. A platinum piece was used as the counter electrode and placed in the anode chamber of the H-type electrolytic cell. Add 31 mL of cathode chamber electrolyte to the cathode chamber, wherein the cathode chamber electrolyte is an aqueous solution (containing 0.1 mol/L HCl and 10 mmol/L benzaldehyde); and add anode chamber electrolyte to the anode chamber, the The electrolyte in the anode chamber is 30mL 0.1mol/L HCl solution. Before electrocatalysis, high-purity argon gas is used to ventilate the sealed cathode electrolysis chamber for 6 minutes to replace all oxygen and air in the solution and above the electrolytic cell with inert argon gas, and then NO is used to electrolyze the sealed cathode. Ventilate the room for 6 minutes. In the electrocatalytic process, electrolysis is carried out using a constant voltage method. The gas flow rate of the NO gas is controlled at about 15 sccm, and the voltage is set to -0.9V vs. RHE. After 3 hours of electrolysis, the electrolyte in the cathode chamber is collected for product analysis. identification. Qualitative analysis was performed by hydrogen nuclear magnetic resonance spectroscopy (H-NMR). The results are shown in Figure 7. Figure 7 is the NMR image of the product of electrocatalytic synthesis of benzylamine. The abscissa of Figure 7 is f1 (ppm). It can be seen from the results of H-NMR that benzylamine can be successfully synthesized with a yield of 36.74%, a Faradaic efficiency of 25.34%, and a selectivity of 77.23%.

Example 9

In this example, commercial carbon cloth is used as a catalyst, benzaldehyde is used as the carbon source, and NH ₂ OH is used as the nitrogen source to synthesize benzylamine through electrocatalysis.

First, clamp commercial carbon cloth on the platinum electrode clip as the working electrode; use the saturated silver/silver chloride electrode as the reference electrode; place the working electrode and reference electrode in the H-type electrolytic cell cathode chamber. A platinum piece was used as the counter electrode and placed in the anode chamber of the H-type electrolytic cell. Add to cathode chamber 30 mL cathode chamber electrolyte, wherein the cathode chamber electrolyte is an aqueous solution (containing 0.1 mol/L HCl, 50 mmol/L benzaldehyde and 300 mmol/L NH ₂ OH); and add the anode chamber electrolyte to the anode chamber , the anode chamber electrolyte is 30mL 0.1mol/L HCl solution. Before electrocatalysis, high-purity argon gas is used to ventilate the sealed cathode electrolytic chamber for 6 minutes to replace all oxygen and air in the solution and above the electrolytic cell with inert argon gas. In the electrocatalytic process, electrolysis is carried out using a constant voltage method. The argon gas flow rate is controlled at about 2 sccm, and the voltage is set to -0.9V vs. RHE. After 4 hours of electrolysis, the electrolyte in the cathode chamber is collected for product identification. . Qualitative analysis was carried out through hydrogen nuclear magnetic resonance spectroscopy (H-NMR). The results are shown in Figure 8. Figure 8 is the NMR spectrum of the product of benzylamine synthesized by electrocatalysis of NH ₂ OH as a nitrogen source. The abscissa of Figure 8 is f1 (ppm). It can be seen from the results of H-NMR that benzylamine can be successfully synthesized with a yield of 25.62%, a Faradaic efficiency of 74.35%, and a selectivity of 98.55%.

Example 10

In this example, commercial carbon cloth is used as a catalyst, furfural is used as the carbon source, and NO is used as the nitrogen source to synthesize furfurylamine through electrocatalysis.

First, clamp commercial carbon cloth on the platinum electrode clip as the working electrode; use the saturated silver/silver chloride electrode as the reference electrode; place the working electrode and reference electrode in the H-type electrolytic cell cathode chamber. A platinum piece was used as the counter electrode and placed in the anode chamber of the H-type electrolytic cell. Add 31 mL of cathode chamber electrolyte to the cathode chamber, wherein the cathode chamber electrolyte is an aqueous solution (containing 0.1 mol/L HCl and 20 mmol/L furfural); and add anode chamber electrolyte to the anode chamber, the anode The chamber electrolyte is 30mL 0.1mol/L HCl solution. Before electrocatalysis, high-purity argon gas is used to ventilate the sealed cathode electrolysis chamber for 6 minutes to replace all oxygen and air in the solution and above the electrolytic cell with inert argon gas, and then NO is used to electrolyze the sealed cathode. Ventilate the room for 6 minutes. In the electrocatalytic process, electrolysis is carried out in a constant voltage manner, the gas flow rate of NO gas is controlled at about 15 sccm, and the voltage is set to -0.9V vs. RHE. After 6 hours of electrolysis, the electrolyte in the cathode chamber is collected for product analysis. identification. Qualitative analysis was carried out through hydrogen nuclear magnetic resonance spectroscopy (H-NMR). The results are shown in Figure 9. Figure 9 is the NMR image of the product of furfurylamine synthesized by NO electrocatalysis as a nitrogen source. The abscissa in Figure 9 is f1 (ppm). It can be seen from the results of H-NMR that furfurylamine can be successfully synthesized with a yield of 25.91%, a Faradaic efficiency of 20.6%, and a selectivity of 29.52%.

Example 11

Preparation of nitrile is carried out in a sealed three-electrode H-type electrolytic cell with the method of the present invention:

In this embodiment, under the action of CoFe-SSM membrane catalyst, 3-methyl-2-oxobutyric acid is used as the carbon source and NO is used as the nitrogen source to synthesize isobutyronitrile through electrocatalysis.

First, a self-made CoFe-SSM membrane was obtained through electrospinning and calcination, and the obtained CoFe-SSM membrane was clamped on a platinum electrode clip as the working electrode; a saturated silver/silver chloride electrode was used as the reference electrode; The working and reference electrodes were placed in the cathode chamber of the H-type electrolytic cell. A platinum piece was used as the counter electrode and placed in the anode chamber of the H-type electrolytic cell. Add 31 mL of cathode chamber electrolyte into the cathode chamber. The cathode chamber electrolyte is an aqueous solution (containing 0.1 mol/L HCl and 40 mmol/L 3- Methyl-2-oxobutyric acid); and add 30 mL of anode chamber electrolyte into the anode chamber, and the anode chamber electrolyte is a 0.1 mol/L HCl solution. Before electrocatalysis, high-purity argon gas is used to ventilate the sealed cathode electrolytic chamber for 6 minutes to replace all oxygen and air in the solution and above the electrolytic cell with inert argon gas. Then use NO to ventilate the sealed cathode electrolytic chamber for 6 minutes. During the electrocatalysis process, the NO gas flow was controlled at about 15 sccm, and electrolysis was performed using a constant voltage method. The voltage was set to -0.6V vs. RHE. After 6 hours of electrolysis, the electrolyte in the cathode chamber was collected for product identification. Qualitative analysis was performed by hydrogen nuclear magnetic resonance spectroscopy (H-NMR). In H-NMR, the spectrum of H atoms on isobutyronitrile is used as the basis for judgment. The results are shown in Figure 10. Figure 10 is the NMR image of the product electrocatalytically synthesized by CoFe-SSM membrane. The abscissa of Figure 10 is f1 (ppm). It can be seen from the H-NMR results that isobutyronitrile can be successfully synthesized with a yield of 25.30%, a Faradaic efficiency of 9.79%, and a selectivity of 80%.

Example 12

In this example, under the action of a commercial carbon cloth catalyst, 3-methyl-2-oxobutyric acid is used as the carbon source and NO is used as the nitrogen source to synthesize isobutyronitrile through electrocatalysis.

First, clamp commercial carbon cloth on the platinum electrode clip as the working electrode; use the saturated silver/silver chloride electrode as the reference electrode; place the working electrode and reference electrode on the cathode of the H-type electrolytic cell room. A platinum piece was used as the counter electrode and placed in the anode chamber of the H-type electrolytic cell. Add 31 mL of cathode chamber electrolyte into the cathode chamber. The cathode chamber electrolyte is an aqueous solution (containing 0.1 mol/L HCl and 40 mmol/L 3-methyl-2-oxobutyric acid); and in the anode chamber Add 30 mL of anode chamber electrolyte, which is a 0.1 mol/L HCl solution. Before electrocatalysis, high-purity argon gas is used to ventilate the sealed cathode electrolytic chamber for 6 minutes to replace all oxygen and air in the solution and above the electrolytic cell with inert argon gas. Then use NO to ventilate the sealed cathode electrolytic chamber for 6 minutes. During the electrocatalysis process, the NO gas flow was controlled at about 15 sccm, and electrolysis was performed using a constant voltage method. The voltage was set to -0.6V vs. RHE. After 6 hours of electrolysis, the electrolyte in the cathode chamber was collected for product identification. Qualitative analysis was performed by hydrogen nuclear magnetic resonance spectroscopy (H-NMR). In H-NMR, the spectrum of H atoms on isobutyronitrile is used as the basis for judgment. The results are shown in Figure 11. Figure 11 is the NMR image of the isobutyronitrile product electrocatalytically synthesized by commercial carbon cloth. The abscissa of Figure 11 is f1 (ppm), it can be seen from the H-NMR results that isobutyronitrile can be successfully synthesized with a yield of 9.20%, a Faradaic efficiency of 3.68%, and a selectivity of 6.25%.

Example 13

In this example, under the action of ZIF-8/PAN membrane catalyst, 3-methyl-2-oxobutyric acid is used as the carbon source and NO is used as the nitrogen source to synthesize isobutyronitrile through electrocatalysis.

First, a self-made ZIF-8/PAN membrane was obtained through electrospinning and calcination, and the resulting ZIF-8/PAN membrane was clamped on a platinum electrode clip as the working electrode; a saturated silver/silver chloride electrode was used as the working electrode. Reference electrode; The working electrode and reference electrode are placed in the cathode chamber of the H-type electrolytic cell. A platinum piece was used as the counter electrode and placed in the anode chamber of the H-type electrolytic cell. Add 31 mL of cathode chamber electrolyte into the cathode chamber. The cathode chamber electrolyte is an aqueous solution (containing 0.1 mol/L HCl and 40 mmol/L 3- Methyl-2-oxobutyric acid); and add 30 mL of anode chamber electrolyte into the anode chamber, and the anode chamber electrolyte is a 0.1 mol/L HCl solution. Before electrocatalysis, high-purity argon gas is used to ventilate the sealed cathode electrolytic chamber for 6 minutes to replace all oxygen and air in the solution and above the electrolytic cell with inert argon gas. Then use NO to ventilate the sealed cathode electrolytic chamber for 6 minutes. During the electrocatalysis process, the NO gas flow was controlled at about 15 sccm, and electrolysis was performed using a constant voltage method. The voltage was set to -0.6V vs. RHE. After 6 hours of electrolysis, the electrolyte in the cathode chamber was collected for product identification. Qualitative analysis was performed by hydrogen nuclear magnetic resonance spectroscopy (H-NMR). In H-NMR, the spectrum of H atoms on isobutyronitrile is used as the basis for judgment. The results are shown in Figure 12. Figure 12 is the NMR image of the product of isobutyronitrile synthesized by ZIF-8/PAN membrane electrocatalysis. Figure 12 The abscissa is f1 (ppm). It can be seen from the H-NMR results that isobutyronitrile can be successfully synthesized with a yield of 22.43%, a Faradaic efficiency of 8.97%, and a selectivity of 37.82%.

Example 14

In this embodiment, under the action of CoFe-SSM membrane catalyst, 4-methyl-2-oxopentanoic acid is used as the carbon source and KNO ₂ is used as the nitrogen source to synthesize isovaleronitrile through electrocatalysis.

First, a self-made CoFe-SSM membrane was obtained through electrospinning and calcination, and the obtained CoFe-SSM membrane was clamped on a platinum electrode clip as the working electrode; a saturated silver/silver chloride electrode was used as the reference electrode; The working and reference electrodes were placed in the cathode chamber of the H-type electrolytic cell. A platinum piece was used as the counter electrode and placed in the anode chamber of the H-type electrolytic cell. Add 31 mL of cathode chamber electrolyte into the cathode chamber. The cathode chamber electrolyte is an aqueous solution (containing 0.1 mol/L HCl, 40 mmol/L 4-methyl-2-oxopentanoic acid and 100 mmol/L KNO ₂ ); and add 30 mL of anode chamber electrolyte into the anode chamber, and the anode chamber electrolyte is a 0.1 mol/L HCl solution. Before electrocatalysis, high-purity argon gas is used to ventilate the sealed cathode electrolytic chamber for 6 minutes to replace all oxygen and air in the solution and above the electrolytic cell with inert argon gas. Then the Ar gas flow was controlled at about 2 sccm, and electrolysis was performed using a constant voltage method. The voltage was set to -0.7V vs. RHE. After 6 hours of electrolysis, the electrolyte in the cathode chamber was collected for product identification. Qualitative analysis was performed by hydrogen nuclear magnetic resonance spectroscopy (H-NMR). In H-NMR, the spectrum of H atoms on isovaleronitrile is used as the basis for judgment. The results are shown in Figure 13. Figure 13 is the NMR spectrum of the electrocatalytic synthesis of isovaleronitrile product using KNO ₂ as a nitrogen source. The horizontal line of Figure 13 The coordinate is f1 (ppm). It can be seen from the H-NMR results that isovaleronitrile can be successfully synthesized with a yield of 18.1%, a Faradaic efficiency of 4.95%, and a selectivity of 20.96%.

Example 15

The present application provides a method for synthesizing amino acids, which is used to solve the technical defects of high energy consumption, long time consumption, and complicated product separation and purification existing in the methods of synthesizing amino acids in the prior art.

Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of this application.

Among them, the raw materials or reagents used in the following examples are all commercially available or homemade.

Please refer to Figure 14. Figure 14 is a schematic diagram of the synthesis route of amino acids provided by this application. Nitrogen oxides such as NO are first electro-reduced to form NH ₃ or NH ₂ OH, and then used as nucleophiles to attack the carbonyl group to obtain Intermediate (imine or oxime), subsequent reduction and hydrogenation to form amino acids. Two reaction paths: ① The condensation of carbonyl compounds with NH ₃ gives imines, followed by electroreduction transfer of 2 electrons and the addition of 2 H ⁺ to form amino acids; ② The condensation of carbonyl compounds with NH ₂ OH yields oximes, followed by electroreduction transfer of 4 electrons and add 4 H ⁺ to form amino acids.

This embodiment provides different porous carbon material catalysts, and their synthesis process is as follows:

1. Iron-based materials (iron single atom material anchored on nitrogen-doped carbon carrier) porous nitrogen-doped carbon material catalyst:

(1) Synthesis of precursor MET-6: 5.0g of ZnCl ₂ is first dissolved in a mixed solution of 50mL ethanol, 75mL deionized water, 20mL ammonia and 50mL N,N-dimethylformamide, and then magnetically stirred to form a uniform solution; then 6.26 mL of 1H-1,2,3-triazole ligand was added dropwise to the above mixed solution, and magnetic stirring was continued at room temperature for 24 hours. Finally, the white product MET-6 was obtained by centrifugation, washing with ethanol and drying at 80°C.

(2) Synthesis of iron-doped MET-6 precursor (Fe-doped MET-6): 10 mg iron acetate is dissolved in 50 mL methanol, 2.0 g precursor MET-6 is dispersed into the above-mentioned iron methanol solution, and then After stirring at 80°C for 8 hours, the iron-doped MET-6 precursor was finally obtained by evaporating the methanol solvent to obtain the iron-doped MET-6 precursor Fe-doped MET-6.

(3) Synthesis of iron single atom material anchored on nitrogen-doped carbon support (Fe SA/NC): Place the Fe-doped MET-6 sample obtained in step (2) on the ceramic tile in a tube furnace Calcined at 950°C for 3 hours under an argon atmosphere, and after cooling to room temperature, a black porous carbon material catalyst doped with iron atoms was obtained, which is an iron single-atom material anchored on a nitrogen-doped carbon carrier, recorded as Fe SA/NC catalyst .

2. Nitrogen-doped porous carbon material catalyst:

Synthesis of nitrogen-doped porous carbon framework (NC): Place the MET-6 sample obtained in step 1 and (1) on a ceramic tile, calcine at 950°C for 3 hours in an argon atmosphere in a tube furnace, and cool to room temperature. Finally, a black porous carbon material catalyst doped with nitrogen atoms was obtained, which was recorded as NC catalyst.

Example 16

In the embodiments of this application, H-NMR (Proton Nuclear Magnetic Resonance Spectroscopy) and LC-MS (High Performance Liquid Chromatography-Mass Spectrometry) tests were performed on the valine standard sample for qualitative and quantitative analysis of valine to confirm Production of valine. Specifically, in the H-NMR spectrum, the H atom on α-C in valine is used as the basis for judgment. In LC-MS, phenyl isothiocyanate (PITC) is used as the derivatization reagent. Under basic conditions of triethylamine, PITC reacts with the N-terminal residue of the amino acid to form a phenylaminothiocarboxyl derivative. The derivative product can be detected by a UV detector in a liquid chromatograph at a wavelength of 254 nm to confirm the formation of the corresponding amino acid.

The H-NMR spectrum of the valine standard sample solution is shown in Figure 15. The H atom on α-C in valine (that is, position a) is used as the basis for judgment. The H at position a is split into two peaks. The corresponding chemical shifts (abscissa) are 3.85ppm and 3.84ppm. The ratio of the peak areas of hydrogen atoms at a, b and c is 1:1:5.99 (approximately 1:1:6), which is consistent with the number of H at the corresponding position of valine.

In LC-MS, valine is derivatized by PITC to obtain the valine derivatized product. Its exact molecular weight is 252.33. After being bombarded in the negative ion mode of electrospray ionization (ESI), a negative ion peak (M-1 peak) with m/z of 251.0 appeared on the LC-MS mass spectrum, as shown in Figure 16, confirming that the PITC derivatization method is suitable for amino acids. detection.

Example 17

The embodiments of this application provide a method for synthesizing amino acids, including the following steps:

The reaction for preparing amino acids in the embodiments of the present application is carried out in a sealed three-electrode H-type electrolytic cell. Under the action of the Fe SA/NC catalyst in Example 15, using 3-methyl-2-oxobutyric acid as the carbon source and NO gas as the nitrogen source, valine was synthesized through electrocatalysis.

First, 1.0 mg of the Fe SA/NC catalyst of Example 15 was evenly supported on a glassy carbon electrode with an area of 1 × 1 cm ² as the working electrode; a saturated silver/silver chloride electrode was used as the reference electrode; these two The root electrode is placed in the cathode chamber of the H-type electrolytic cell. A platinum sheet serves as the counter electrode and is placed in the anode chamber of the H-type electrolytic cell. 30 mL of electrolyte solution (containing 0.1 M HCl and 20 mM 3-methyl-2-oxobutyric acid) was added to the cathode chamber, and 30 mL of 0.1 M HCl solution was added to the anode chamber as the electrolyte solution. Before electrocatalysis, first use high-purity argon gas to ventilate the sealed cathode electrolytic chamber for 10 minutes to replace all oxygen and air in the solution and above the electrolytic cell with inert argon gas, and then vent NO gas into the solution for 10 minutes. Saturate, and use a quality control flow meter to maintain a flow rate of 20 mL min ^{-1 and} continuously introduce NO gas. In the electrocatalytic process, electrolysis is carried out using a constant voltage method. The voltage is set to -0.6V vs. RHE. After electrolysis for 4 hours, 5 hours and 6 hours, the electrolyte in the cathode chamber under different electrolysis times is collected to analyze the products. Identification (4-hour product, 5-hour product and 6-hour product respectively). The synthesized amino acids were characterized and quantified by hydrogen nuclear magnetic resonance spectroscopy (H-NMR) and high-performance liquid chromatography-mass spectrometry (LC-MS). In H-NMR, the spectrum of the H atom on α-C in the amino acid is used as the basis for judgment; in LC-MS, this example uses phenyl isothiocyanate (PITC) as the derivatization reagent, in triethylamine Under alkaline conditions, PITC reacts with the N-terminal residue of the amino acid to form an phenylaminothiocarboxyl derivative, which can be detected by a UV detector in liquid chromatography at a wavelength of 254 nm.

In the above-mentioned electrocatalytic synthesis of amino acids, the voltage was constantly set to -0.6V vs. RHE. After the electrolysis time was 4 hours, 5 hours, and 6 hours, the electrolyte in the cathode chamber was collected for product identification. After detection by H-NMR and LC-MS (Figure 17 and Figure 18, the abscissa of Figure 17 is f1 (ppm)), in H-NMR, it can be seen that corresponding peaks appear at a, b and c, and The chemical shift is consistent with the valine standard, confirming the successful synthesis of valine. At the same time, the H atom on α-C of valine (i.e., position a) is split into a double peak, and the corresponding chemical shifts are 3.85ppm and 3.84ppm, which is consistent with its structure; and the intensity of its double peak changes with the electrolysis The increase in time gradually increased, indicating that the production of valine was gradually increasing. In LC-MS, there is a negative ion peak (M-1 peak) with m/z of 251.0, which is the negative ion peak of the valine derivatization product, which confirms the generation of valine, which is consistent with the H-NMR results. evidence. At the same time, there is still a raw material (3-methyl-2-oxobutyric acid) for preparing valine through electrocatalytic reductive amination.

According to the above H-NMR test results under different electrolysis times and the peak area integration ratio of the corresponding peak to the internal standard DMSO, as shown in Figure 19, the raw material material (3-methyl-2) for preparing valine under different electrolysis times was calculated. -oxybutyric acid) conversion rate. As shown in Figure 20, the raw material for preparing valine (3-methyl The conversion rate of methyl-2-oxobutyric acid) continued to increase with the increase of potential, reaching 73.49% after 6 hours of reaction at -0.6V vs. RHE potential.

Example 18

The examples of this application prepare valine with reference to the method of Example 17, including the following steps:

The method for preparing valine in this embodiment is as in Example 3, except that 20mM 3-methyl-2-oxobutyric acid and 30mM 3-methyl-2-oxobutyric acid are used, and the flow rate is 20mL min ^-1 , 30 mL min ^-1 of NO gas was used as the carbon source and nitrogen source respectively, and electrolysis was performed at -0.6 V vs. RHE potential for 4 hours and 6 hours. The remaining parameters and steps were consistent with Example 17. Then collect the electrolyte in the cathode chamber for H-NMR analysis (Figure 21).

Example 19

The method for preparing valine in this example is as in Example 17. The difference is that different potentials (-0.6V vs. RHE and -0.8V vs. RHE) are applied to the electrocatalytic synthesis of valine, and the reaction time is 4 hours. and 6 hours for electrocatalysis; other parameters and steps are consistent with Example 17, and the electrolyte in the cathode chamber is collected for product identification. After qualitative and quantitative detection by H-NMR, the results are shown in Figure 22 (the abscissa of Figure 22 is f1 (ppm)).

Example 20

The reaction for preparing amino acids in the embodiments of the present application is carried out in a sealed three-electrode H-type electrolytic cell. Under the action of the Fe SA/NC catalyst of Example 1, using pyruvate as the carbon source and 500 mM KNO ₃ as the nitrogen source, alanine was synthesized through electrocatalysis.

First, 1.0 mg of the Fe SA/NC catalyst of Example 15 was evenly supported on a glassy carbon electrode with an area of 1 × 1 cm ² as the working electrode; a saturated silver/silver chloride electrode was used as the reference electrode; these two The root electrode is placed in the cathode chamber of the H-type electrolytic cell. A platinum sheet serves as the counter electrode and is placed in the anode chamber of the H-type electrolytic cell. Add 30 mL of electrolyte solution (containing 0.1 M HCl and 20 mM pyruvic acid, and then add 500 mM KNO ₃ ) to the cathode chamber, and add 30 mL of 0.1 M HCl solution as the electrolyte to the anode chamber. Before electrocatalysis, high-purity argon gas is used to ventilate the sealed cathode electrolytic chamber for 10 minutes to replace all oxygen and air in the solution and above the electrolytic cell with inert argon gas. In the electrocatalytic process, electrolysis is carried out using a constant voltage method, and the voltage is set to -0.6V vs. RHE. After 6 hours of electrolysis, the electrolyte in the cathode chamber is collected for product identification. Qualitative analysis was performed by hydrogen nuclear magnetic resonance spectroscopy (H-NMR). In H-NMR, the spectrum of H atoms on α-C in amino acids is used as the basis for judgment. The results are shown in Figure 23 (the abscissa of Figure 23 is f1 (ppm)). It can be seen from the results of H-NMR that alanine Acid can be synthesized successfully.

Example 21

The reaction for preparing amino acids in the embodiments of the present application is carried out in a sealed three-electrode H-type electrolytic cell. Under the action of the Fe SA/NC catalyst in Example 15, using pyruvic acid as the carbon source and 500 mM KNO ₂ As a nitrogen source, alanine is synthesized via electrocatalysis.

First, 1.0 mg of the NC catalyst of Example 15 was evenly supported on a glassy carbon electrode with an area of 1 × 1 cm ² as the working electrode; a saturated silver/silver chloride electrode was used as the reference electrode; these two electrodes were placed In the cathode compartment of an H-type electrolytic cell. A platinum sheet serves as the counter electrode and is placed in the anode chamber of the H-type electrolytic cell. Add 30 mL of electrolyte solution (containing 0.1 M HCl and 20 mM pyruvic acid, followed by 500 mM KNO ₂ ) into the cathode chamber, and add 30 mL of 0.1 M HCl solution as the electrolyte into the anode chamber. Before electrocatalysis, high-purity argon gas is used to ventilate the sealed cathode electrolytic chamber for 10 minutes to replace all oxygen and air in the solution and above the electrolytic cell with inert argon gas. In the electrocatalytic process, electrolysis is carried out using a constant voltage method, and the voltage is set to -0.6V vs. RHE. After 6 hours of electrolysis, the electrolyte in the cathode chamber is collected for product identification. Qualitative analysis was performed by hydrogen nuclear magnetic resonance spectroscopy (H-NMR). In H-NMR, the spectrum of H atoms on α-C in amino acids is used as the basis for judgment. The results are shown in Figure 24 (the abscissa of Figure 24 is f1 (ppm)). It can be seen from the results of H-NMR that valine Acid can be synthesized successfully.

Example 22

The examples of this application prepare amino acids according to the method of Example 17, including the following steps:

In this example, the method for preparing valine is referred to Example 17. The difference is that 4-methyl-2-oxopentanoic acid is replaced by 3-methyl-2-oxopentanoic acid in Example 17. At -0.7V vs. The electrocatalytic reaction was carried out at RHE potential for 2 hours; other parameters and steps were consistent with Example 17. The electrolyte in the cathode chamber was collected for product identification. The synthesized amino acids were characterized by hydrogen nuclear magnetic resonance spectroscopy (H-NMR) and high-performance liquid chromatography-mass spectrometry (LC-MS). In this example, leucine was electrocatalytically synthesized. The results are shown in Figure 25 (abscissa in Figure 25 is f1 (ppm)) and as shown in Figure 26, it can be seen from the H-NMR results that leucine can be successfully synthesized.

Example 23

In this example, the method for preparing valine is referred to Example 17. The difference is that 3-methyl-2-oxopentanoic acid is substituted for 3-methyl-2-oxobutyric acid in Example 17, and the temperature is -0.6V. The electrocatalytic reaction was carried out at vs. RHE potential for 2 hours; other parameters and steps were consistent with Example 17. The electrolyte in the cathode chamber was collected for product identification. High-performance liquid chromatography-mass spectrometry (LC-MS) was used to characterize the synthesized amino acids. In this example, isoleucine was electrocatalytically synthesized. The results are shown in Figure 27. It can be seen from the LC-MS results that isoleucine can Successfully synthesized.

Example 24

In this example, the method for preparing valine is referred to Example 17. The difference is that phenylpyruvic acid is replaced with 3-methyl-2-oxobutyric acid in Example 17, and electrocatalysis is performed at -0.6V vs. RHE potential. ; The remaining parameters and steps are consistent with Example 17, and the electrolyte in the cathode chamber is collected for product identification. High-performance liquid chromatography-mass spectrometry (LC-MS) was used to characterize the synthesized amino acids. In this example, phenylalanine was electrocatalytically synthesized. The results are shown in Figure 28. It can be seen from the LC-MS results that phenylalanine can be successfully synthesized.

Example 25

In this example, the method for preparing valine is referred to Example 17. The difference is that pyruvic acid is replaced with 3-methyl-2-oxobutyric acid in Example 17, and the electrocatalytic reaction is performed at -0.8V vs. RHE potential. 2 hours; other parameters and steps are consistent with Example 17, and the electrolyte in the cathode chamber is collected for product identification. The synthesized amino acids were characterized by hydrogen nuclear magnetic resonance spectroscopy (H-NMR) and high-performance liquid chromatography-mass spectrometry (LC-MS). In this example, alanine was electrocatalytically synthesized. The results are shown in Figure 29 (the abscissa of Figure 29 is f1 (ppm)) and as shown in Figure 30, it can be seen from the results of H-NMR and LC-MS that alanine can be successfully synthesized.

Example 26

In this example, the method for preparing valine is referred to Example 17. The difference is that glyoxylic acid is replaced with 3-methyl-2-oxobutyric acid in Example 17, and the electrolysis is performed at -0.6V vs. RHE potential. The catalytic reaction was carried out for 2 hours; other parameters and steps were consistent with Example 17. The electrolyte in the cathode chamber was collected for product identification. The synthesized amino acids were characterized by hydrogen nuclear magnetic resonance spectroscopy (H-NMR) and high-performance liquid chromatography-mass spectrometry (LC-MS). In this example, glycine was electrocatalytically synthesized. The results are shown in Figure 31 (the abscissa of Figure 31 is f1 (ppm)) and as shown in Figure 32, it can be seen from the LC-MS results that glycine can be successfully synthesized.

Example 27

In this example, the method for preparing valine is referred to Example 17. The difference is that α-ketoglutarate is replaced with 3-methyl-2-oxobutyric acid in Example 17, and the potential is -0.8V vs. RHE respectively. The electrocatalytic reaction was carried out for 2 hours; the other parameters and steps were consistent with Example 17, and the electrolyte in the cathode chamber was collected for product identification. High-performance liquid chromatography-mass spectrometry (LC-MS) was used to characterize the synthesized amino acids. In this example, glutamic acid was electrocatalytically synthesized. The results are shown in Figure 33. It can be seen from the LC-MS results that glutamic acid can be successfully synthesis.

Example 28

In this example, the method for preparing valine is referred to Example 17. The difference is that oxaloacetic acid is replaced with 3-methyl-2-oxobutyric acid in Example 17, and the electrolysis is performed at -0.7V vs. RHE potential. Catalysis; other parameters and steps are consistent with Example 17, and the electrolyte in the cathode chamber is collected for product identification. The synthesized amino acids were characterized by hydrogen nuclear magnetic resonance spectroscopy (H-NMR) and high-performance liquid chromatography-mass spectrometry (LC-MS). In this example, aspartic acid was electrocatalytically synthesized. The results are shown in Figure 34 (crossbar of Figure 34 The coordinates are f1 (ppm)) and shown in Figure 35. It can be seen from the results of H-NMR and LC-MS that aspartic acid can be successfully synthesized.

Example 29

In this example, the method for preparing valine is referred to Example 17. The difference is that 2-butyruvic acid is substituted for 3-methyl-2-oxobutyric acid in Example 17, and the conditions are -0.7V vs. RHE potential respectively. perform electrocatalysis The reaction lasted for 2 hours; other parameters and steps were consistent with Example 17. The electrolyte in the cathode chamber was collected for product identification. The synthesized amino acids were characterized by hydrogen nuclear magnetic resonance spectroscopy (H-NMR) and high-performance liquid chromatography-mass spectrometry (LC-MS). In this example, aminobutyric acid was electrocatalytically synthesized. The results are shown in Figure 36 (the abscissa of Figure 36 is f1 (ppm)) and as shown in Figure 37, it can be seen from the results of H-NMR and LC-MS that aminobutyric acid can be successfully synthesized.

In summary, the results of the examples of this application illustrate that nitrogen oxides are used as nitrogen sources, electrocatalytically reduced to form NH ₃ or NH ₂ OH is used as a nucleophile to attack the carbonyl group in the α-keto acid, and then reduced and hydrogenated to form an amino acid. The applied synthesis method uses cheap porous carbon material catalysts doped with heteroatoms, such as doped iron, copper, nitrogen, etc., which can avoid the use of precious metal and toxic metal catalysts to obtain amino acids. Therefore, the applied method can utilize electricity and water. As energy and hydrogen energy respectively, clean energy is used to electrocatalyze the conversion of nitrogen-containing oxides in exhaust gas and wastewater to synthesize amino acids.

Example 30

Synthesis of CoFe-PBA precursor: Dissolve a certain amount of 15.0mmol CoCl ₂ ·6H ₂ O and a certain amount of 22.5mmol sodium citrate dihydrate in 500mL deionized water to obtain liquid A; dissolve a certain amount of 10mmol ferricyanide Dissolve the potassium phosphate evenly in 500 mL of deionized water to obtain liquid B; under magnetic stirring, quickly introduce liquid B into liquid A, stir for 10 minutes and let stand for 24 hours, then centrifuge the obtained product, and mix with water and Wash each with ethanol three times, and continue centrifugation to obtain the CoFe-PBA precursor. The obtained CoFe-PBA precursor was material characterized, and the results are shown in Figures 38 to 40. Figure 38 is the XRD pattern of the CoFe-PBA precursor. Figure 39 is the SEM image of the CoFe-PBA precursor. Figure 40 is TEM image of CoFe-PBA precursor.

Preparation of CoFe-PBA/PAN membrane: Mix the above synthesized CoFe-PBA precursor with polyacrylonitrile (PAN) and N,N-dimethylformamide (DMF) and stir evenly to obtain a mass fraction of 6wt% to 15wt % of the electrospinning solution. The electrospinning solution is subjected to an electrospinning process to prepare a CoFe-PBA/PAN membrane.

Preparation of CoFe/NC carbon fiber membrane: The CoFe-PBA/PAN membrane obtained above was first pre-oxidized in the air at 220°C for 3 hours, and then calcined at 800°C for 2 hours in an argon atmosphere to obtain the CoFe/NC carbon fiber membrane. The obtained CoFe/NC carbon fiber membrane was material characterized, and the results are shown in Figures 41 to 45. Figure 41 is the XRD pattern of the CoFe/NC carbon fiber film, Figure 42 is the SEM image of the CoFe/NC carbon fiber film, and Figure 43 is TEM image of the CoFe/NC carbon fiber membrane. Figure 44 is the nitrogen adsorption and desorption curve of the CoFe/NC carbon fiber membrane. Figure 45 is the pore size distribution of the CoFe/NC carbon fiber membrane. It can be seen that the CoFe/NC carbon fiber membrane has a hierarchical pore structure with micropores (1.2nm) and mesopores (2.7nm and 5.1nm) coexisting, with a specific surface area of 371.25m ² g ^-1 and a pore volume of 0.473cm ³ g ^-1 , the average pore diameter is 5.095nm.

Example 31

Synthesis of NiFe-PBA precursor: Dissolve a certain amount of 15.0mmol NiCl ₂ ·6H ₂ O and a certain amount of 22.5mmol sodium citrate dihydrate in 500mL deionized water to obtain liquid A; add a certain amount of 10mmol ferricyanide Dissolve potassium acid evenly in 500mL deionized water to obtain liquid B; under magnetic Under stirring, quickly introduce the B solution into the A solution, stir for 10 minutes and then let it stand for 24 hours. Then, the obtained product is centrifuged, washed three times with water and ethanol, and centrifuged further to obtain the NiFe-PBA precursor.

Preparation of NiFe-PBA/PAN membrane: Mix and stir the NiFe-PBA precursor synthesized above with polyacrylonitrile (PAN) and N,N-dimethylformamide (DMF) evenly to obtain a mass fraction of 6 to 15 wt% electrospinning solution between. The electrospinning solution is subjected to an electrospinning process to prepare a NiFe-PBA/PAN membrane. Preparation of NiFe/NC carbon fiber membrane: The NiFe-PBA/PAN membrane obtained above was first pre-oxidized in air at 220°C for 3 hours, and then calcined at 800°C for 2 hours in an argon atmosphere to obtain the NiFe/NC carbon fiber membrane.

Example 32

Synthesis of FeFe-PBA precursor: Dissolve a certain amount of 15.0mmol FeCl ₂ ·6H ₂ O and a certain amount of 22.5mmol sodium citrate dihydrate in 500mL deionized water to obtain liquid A; add a certain amount of 10mmol ferricyanide Dissolve the potassium phosphate evenly in 500 mL of deionized water to obtain liquid B; under magnetic stirring, quickly introduce liquid B into liquid A, stir for 10 minutes and let stand for 24 hours, then centrifuge the obtained product, and mix with water and Wash each with ethanol three times, and continue centrifugation to obtain the FeFe-PBA precursor.

Preparation of FeFe-PBA/PAN membrane: Mix the above synthesized FeFe-PBA precursor with polyacrylonitrile (PAN) and N,N-dimethylformamide (DMF) and stir evenly to obtain a mass fraction of 6-15wt% electrospinning solution between. The electrospinning solution is subjected to an electrospinning process to prepare a FeFe-PBA/PAN membrane. Preparation of FeFe/NC carbon fiber membrane: The FeFe-PBA/PAN membrane obtained above was first pre-oxidized in the air at 220°C for 3 hours, and then calcined at 800°C for 2 hours in an argon atmosphere to obtain the FeFe/NC carbon fiber membrane.

Example 33

Synthesis of CoCo-PBA precursor: Dissolve a certain amount of 15.0mmol CoCl ₂ ·6H ₂ O and a certain amount of 22.5mmol sodium citrate dihydrate in 500mL deionized water to obtain liquid A; dissolve a certain amount of 10mmol cobalt cyanide Dissolve the potassium phosphate evenly in 500 mL of deionized water to obtain liquid B; under magnetic stirring, quickly introduce liquid B into liquid A, stir for 10 minutes and let stand for 24 hours, then centrifuge the obtained product, and mix with water and Wash each with ethanol three times, and continue centrifugation to obtain the CoCo-PBA precursor.

Preparation of CoCo-PBA/PAN membrane: Mix the above synthesized CoCo-PBA precursor with polyacrylonitrile (PAN) and N,N-dimethylformamide (DMF) and stir evenly to obtain a mass fraction of 6-15wt% electrospinning solution between. The electrospinning solution is subjected to an electrospinning process to prepare a CoCo-PBA/PAN membrane.

Preparation of CoCo/NC carbon fiber membrane: The CoCo-PBA/PAN membrane obtained above was first pre-oxidized in the air at 220°C for 3 hours, and then calcined at 800°C for 2 hours in an argon atmosphere to obtain the CoCo/NC carbon fiber membrane.

Example 34

Using the CoFe/NC carbon fiber membrane obtained in Example 30 as a catalyst, it was prepared by electrochemical catalysis Amino acids, the reaction is carried out in a sealed three-electrode H-type electrolytic cell.

First, the CoFe/NC carbon fiber membrane (i.e., the metal-loaded nitrogen-doped carbon fiber membrane material) is used as the working electrode; the saturated silver/silver chloride electrode is used as the reference electrode; the working electrode and the reference electrode Placed in the cathode chamber of the H-type electrolytic cell. A platinum sheet was used as a counter electrode, which was placed in the anode chamber of the H-type electrolytic cell.

Add 30 mL of cathode chamber electrolyte into the cathode chamber of the above H-type electrolytic cell. The cathode chamber electrolyte contains HCl with a concentration of 0.1 mol/L and 4-methyl-2 with a slowly added concentration of 40 mmol/L. - Oxopentanoic acid; add 30 mL of anode chamber electrolyte into the anode chamber of the above-mentioned H-type electrolytic cell, and the anode chamber electrolyte is an HCl solution with a concentration of 0.1 mol/L.

Before electrocatalysis, first use high-purity argon gas to ventilate the sealed cathode chamber for 10 minutes to replace all oxygen and air in the solution and above the electrolytic cell with inert argon gas, and then vent NO gas for 5 minutes until the solution is saturated. , and use a quality control flow meter to maintain a flow rate of 15mL/min to continuously introduce NO gas. In the electrocatalytic process, electrolysis is carried out using a constant voltage method. The voltage setting range is from -0.5V vs. RHE to -1.1V vs. RHE. After 6 hours of electrolysis, the electrolyte in the cathode chamber is collected for product identification.

The synthesized amino acids were characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of H atoms on α-C in the amino acids was used as the basis for judgment. The results are shown in Figure 46. Figure 46 H-NMR spectrum of leucine synthesized after electrolysis for 6 hours using CoFe/NC carbon fiber membrane as catalyst under the potential condition of -0.9V vs. RHE. The selectivity results of the product are shown in Figure 47. Figure 47 is a histogram of the selectivity of leucine after electrolysis for 6 hours using CoFe/NC carbon fiber membrane as a catalyst at different potentials; the Faradaic efficiency and yield results of leucine are as follows As shown in Figure 48, Figure 48 is a histogram of Faradaic efficiency and yield of leucine after electrolysis for 6 hours using CoFe/NC carbon fiber membrane as a catalyst at different potentials. It can be seen from Figures 46 to 48 that leucine was successfully synthesized in this embodiment; the selectivity of leucine was as high as 53.49%, the Faradaic efficiency reached 31.09%, and the yield was 121.989 μmol/h.

CoFe/NC carbon fiber membrane (i.e., metal-loaded nitrogen-doped carbon fiber membrane material) electrocatalytically synthesizes amino acids under the above experimental conditions. It has ultra-long cycle stability and can still maintain its resistance to nitrogen oxides after 40 cycles for a total of 240 hours. High catalytic activity, high selectivity and high yield for the synthesis of leucine. As shown in Figure 49, Figure 49 is a long cycle stability test chart of leucine synthesis using CoFe/NC carbon fiber membrane as a catalyst. Figure 49 shows the ultra-long cycle stability of leucine synthesis using CoFe/NC carbon fiber membrane as a catalyst.

Example 35

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 was that the NO gas was replaced with NO ₂ gas of 15 mL/min.

The synthesized amino acids are characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of the H atom on α-C in the amino acid is used as the basis for judgment. The results are shown in Figure 50. Figure 50 The H-NMR spectrum of the leucine synthesized after electrolysis for 6 hours using the CoFe/NC carbon fiber membrane as the catalyst and 15 mL/min NO ₂ gas as the nitrogen source under the potential condition of -0.7V vs. RHE. As can be seen from Figure 50, this example successfully synthesized leucine; among them, the selectivity of leucine was 11.2%, and the yield reached to 15.7μmol/h.

Example 36

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 was that the NO gas was replaced with 100 mmol/L KNO ₂ .

The synthesized amino acids were characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of H atoms on α-C in the amino acids was used as the basis for judgment. The results are shown in Figure 51. Figure 51 H-NMR spectrum of leucine synthesized after electrolysis for 6 hours using CoFe/NC carbon fiber membrane as catalyst and 100 mmol/L KNO ₂ as nitrogen source under the potential condition of -0.7V vs. RHE. As can be seen from Figure 51, leucine was successfully synthesized in this example; the selectivity of leucine was 23.23%, and the yield reached 39.56 μmol/h.

Example 37

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 is that the NO gas was replaced with 1 mol/L KNO ₃ and the 40 mmol/L 4-methyl-2-oxopentanoic acid was replaced with 20 mmol/L 4-Methyl-2-oxopentanoic acid.

The synthesized amino acids are characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of the H atom on α-C in the amino acid is used as the basis for judgment. The results are shown in Figure 52. Figure 52 H-NMR spectrum of leucine synthesized after electrolysis for 3 hours using CoFe/NC carbon fiber membrane as catalyst and 1 mol/L KNO ₃ as nitrogen source under the potential condition of -1.1V vs. RHE. As can be seen from Figure 52, leucine was successfully synthesized in this example; the selectivity of leucine was 27.84%, and the yield reached 26.28 μmol/h.

Example 38

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 was that the CoFe/NC carbon fiber membrane obtained in Example 30 was replaced with the FeFe/NC carbon fiber membrane obtained in Example 32 as the catalyst.

The synthesized amino acids were characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of H atoms on α-C in the amino acids was used as the basis for judgment. The results are shown in Figure 53. Figure 53 H-NMR spectrum of leucine synthesized after electrolysis for 6 hours using FeFe/NC carbon fiber membrane as catalyst under the potential condition of -0.7V vs. RHE.

As can be seen from Figure 53, leucine was successfully synthesized in this example; the selectivity of leucine was 39.56%, the Faradaic efficiency reached 22.85%, and the yield reached 62.80 μmol/h. It can be seen that the metal-loaded porous carbon fiber membrane also has the property of efficient electrocatalytic synthesis of amino acids.

Example 39

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 was that the CoFe/NC carbon fiber membrane obtained in Example 30 was replaced with the CoCo/NC carbon fiber membrane obtained in Example 33 as the catalyst.

The synthesized amino acids were characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of H atoms on α-C in the amino acids was used as the basis for judgment. The results are shown in Figure 54, Figure 54 This is the H-NMR spectrum of leucine synthesized after electrolysis for 6 hours using CoCo/NC carbon fiber membrane as a catalyst under the potential condition of -0.7V vs. RHE. As can be seen from Figure 54, leucine was successfully synthesized in this example; the selectivity of leucine was 40.82%, the Faradaic efficiency reached 25.52%, and the yield reached 74.86 μmol/h. It can be seen that the metal-loaded porous carbon fiber membrane also has the property of efficient electrocatalytic synthesis of amino acids.

Example 40

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 is that the 40mmol/L 4-methyl-2-oxopentanoic acid in the cathode chamber electrolyte was replaced with 20mmol/L 3-methyl-2 -Oxyvaleric acid.

The synthesized amino acids are characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of the H atom on α-C in the amino acid is used as the basis for judgment. The results are shown in Figure 55 and Figure 45. H-NMR spectrum of isoleucine synthesized after electrolysis for 6 hours under the potential conditions of -0.7V vs. RHE. As can be seen from Figure 55, isoleucine was successfully synthesized in this example; the selectivity of isoleucine was 19.90%, the Faradaic efficiency reached 5.00%, and the yield reached 20.57 μmol/h.

Example 41

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 is that 40mmol/L of 4-methyl-2-oxopentanoic acid in the cathode chamber electrolyte was replaced by 40mmol/L of 3-methyl-2 - Oxybutyric acid.

The synthesized amino acids were characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of H atoms on α-C in the amino acids was used as the basis for judgment. The results are shown in Figure 56. Figure 56 H-NMR spectrum of valine synthesized after electrolysis for 6 hours under the potential conditions of -0.7V vs. RHE. As can be seen from Figure 56, valine was successfully synthesized in this example; the selectivity of valine was 12.37%, the Faradaic efficiency reached 5.25%, and the yield reached 25.27 μmol/h.

Example 42

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 was that 40 mmol/L 4-methyl-2-oxopentanoic acid in the cathode chamber electrolyte was replaced with 40 mmol/L pyruvate.

The synthesized amino acids were characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of H atoms on α-C in the amino acids was used as the basis for judgment. The results are shown in Figure 57. Figure 57 H-NMR spectrum of alanine synthesized after electrolysis for 6 hours under the potential conditions of -0.7V vs. RHE. As can be seen from Figure 57, alanine was successfully synthesized in this example; the selectivity of alanine was 74.13%, the Faradaic efficiency reached 38.15%, and the yield reached 153.2 μmol/h.

Example 43

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 is that 40mmol/L of 4-methyl-2-oxopentanoic acid in the cathode chamber electrolyte was replaced by 40mmol/L of α-ketoglutaric acid. .

The synthesized amino acids are characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of the H atom on α-C in the amino acid is used as the basis for judgment. The results are shown in Figure 58. Figure 58 H-NMR spectrum of glutamic acid synthesized after electrolysis for 6 hours under the potential condition of -0.7V vs. RHE. As can be seen from Figure 58, glutamic acid was successfully synthesized in this embodiment; the selectivity of glutamic acid was 48.30%, the Faradaic efficiency reached 24.10%, and the yield reached 99.82 μmol/h.

Example 44

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 was that 40 mmol/L 4-methyl-2-oxopentanoic acid in the cathode chamber electrolyte was replaced with 40 mmol/L oxaloacetic acid.

The synthesized amino acids are characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of H atoms on α-C in the amino acids is used as the basis for judgment. The results are shown in Figure 59. Figure 59 H-NMR spectrum of aspartic acid synthesized after electrolysis for 6 hours under the potential conditions of -0.7V vs. RHE. As can be seen from Figure 59, aspartic acid was successfully synthesized in this example; the selectivity of aspartic acid was 29.96%, the Faradaic efficiency reached 17.00%, and the yield reached 61.92 μmol/h.

Example 45

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 was that 40 mmol/L 4-methyl-2-oxopentanoic acid in the cathode chamber electrolyte was replaced with 40 mmol/L glyoxylic acid.

The synthesized amino acids were characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of H atoms on α-C in the amino acids was used as the basis for judgment. The results are shown in Figure 60. Figure 60 H-NMR spectrum of glycine synthesized after electrolysis for 6 hours under the potential conditions of -0.7V vs. RHE. It can be seen from Figure 60 that glycine was successfully synthesized in this embodiment; the selectivity of glycine was 79.55%, the Faradaic efficiency reached 41.22%, and the yield reached 164.42 μmol/h.

Example 46

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 was that 40 mmol/L 4-methyl-2-oxopentanoic acid in the cathode chamber electrolyte was replaced with 40 mmol/L 2-butyruvic acid.

The synthesized amino acids were characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of H atoms on α-C in the amino acids was used as the basis for judgment. The results are shown in Figure 61. Figure 61 H-NMR spectrum of 2-aminobutyric acid synthesized after electrolysis for 6 hours under the potential conditions of -0.7V vs. RHE. As can be seen from Figure 61, 2-aminobutyric acid was successfully synthesized in this example; the selectivity of 2-aminobutyric acid was 82.61%, the Faradaic efficiency reached 41.61%, and the yield reached 164.24 μmol/h.

Example 47

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 was that 40 mmol/L of 4-methyl-2-oxopentanoic acid in the cathode chamber electrolyte was replaced by 40 mmol/L of 2-pentanoic acid.

The synthesized amino acids were characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of H atoms on α-C in the amino acids was used as the basis for judgment. The results are shown in Figure 62. Figure 62 H-NMR spectrum of 2-aminovaleric acid synthesized after electrolysis for 6 hours under the potential conditions of -0.7V vs. RHE. As can be seen from Figure 62, this example successfully synthesized 2-aminovaleric acid; the selectivity of 2-aminovaleric acid was 61.85%, the Faradaic efficiency reached 29.31%, and the yield reached 115.84 μmol/h.

Example 48

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 is that the 40mmol/L 4-methyl-2-oxopentanoic acid in the cathode chamber electrolyte was replaced with 40mmol/L 2-oxohexanoic acid. .

The synthesized amino acids were characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of H atoms on α-C in the amino acids was used as the basis for judgment. The results are shown in Figure 63, Figure 63 This is the H-NMR spectrum of 2-aminocaproic acid synthesized after electrolysis for 6 hours under the potential condition of -0.7V vs. RHE. As can be seen from Figure 63, 2-aminocaproic acid was successfully synthesized in this example; the selectivity of 2-aminocaproic acid was 45.71%, the Faradaic efficiency reached 21.66%, and the yield reached 89.11 μmol/h.

Example 49

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 is that 40mmol/L of 4-methyl-2-oxopentanoic acid in the cathode chamber electrolyte was replaced by 40mmol/L of 2-cyclobutyl- 2-Carbonylacetic acid.

The synthesized amino acids are characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of the H atom on α-C in the amino acid is used as the basis for judgment. The results are shown in Figure 74. Figure 74 H-NMR spectrum of 2-amino-cyclobutylacetic acid synthesized after electrolysis for 6 hours under the potential conditions of -0.7V vs. RHE.

As can be seen from Figure 64, this example successfully synthesized 2-amino-cyclobutylacetic acid; among them, the selectivity of 2-amino-cyclobutylacetic acid was 31.30%, the Faradaic efficiency reached 16.62%, and the yield reached 55.75 μmol/h. .

Example 50

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 is that the 40mmol/L 4-methyl-2-oxopentanoic acid in the cathode chamber electrolyte was replaced with 20mmol/L 2-oxo-4. -Phenylbutyric acid.

The synthesized amino acids are characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of H atoms on α-C in the amino acids is used as the basis for judgment. The results are shown in Figure 65. Figure 65 H-NMR spectrum of homophenylalanine synthesized after electrolysis for 6 hours under the potential conditions of -0.9V vs. RHE. As can be seen from Figure 65, this example successfully synthesized homophenylalanine; the selectivity of homophenylalanine was 87.77%, the Faradaic efficiency reached 18.67%, and the yield reached 90.68 μmol/h.

Example 51

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 was that 40 mmol/L 4-methyl-2-oxopentanoic acid in the cathode chamber electrolyte was replaced with 40 mmol/L benzoylformic acid.

The synthesized amino acids were characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of H atoms on α-C in the amino acids was used as the basis for judgment. The results are shown in Figure 66. Figure 66 H-NMR spectrum of phenylglycine synthesized after electrolysis for 6 hours under the potential conditions of -0.9V vs. RHE. As can be seen from Figure 66, phenylglycine was successfully synthesized in this example; the selectivity of phenylglycine was 6.52%, the Faradaic efficiency reached 3.22%, and the yield reached 13.47 μmol/h.

By replacing α-keto acid with other amino acid precursors, and under certain experimental conditions, using metal-loaded nitrogen-doped carbon fiber membrane materials as electrocatalysts, electrocatalytic artificial synthesis of up to 13 amino acids can be achieved, covering essential amino acids for the human body. There are three categories of non-essential amino acids for the human body and amino acids not involved in protein synthesis. Different types of amino acids that can be electrocatalytically synthesized using different α-keto acid compounds are shown in Table 3.

table 3

Example 52

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 is that the 40mmol/L 4-methyl-2-oxopentanoic acid in the cathode chamber electrolyte was replaced with 150mmol/L 4-methyl-2 - Oxopentanoic acid, the potential of -0.7V vs.RHE is changed to -0.9V vs.RHE.

After 24 hours of electrolysis reaction, the catholyte was freeze-dried and purified to obtain 1.30g of leucine product. The results are shown in Figure 67. Figure 67 shows the electrolysis after 24 hours of continuous electrolysis under the potential condition of -0.9V vs. RHE. Photo of the synthesized leucine after purification.

The synthesized amino acids are characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of H atoms on α-C in the amino acids is used as the basis for judgment. The results are shown in Figure 68. Figure 68 H-NMR spectrum of the purified leucine synthesized after continuous electrolysis for 24 hours under the potential condition of -0.9V vs. RHE. As can be seen from Figure 68, leucine was successfully synthesized in this embodiment; the purity of the synthesized leucine was 92%.

Comparative example 1

Amino acids were synthesized according to the method of Example 34. The difference from Example 34 was that the CoFe/NC carbon fiber film was replaced with CoFe alloy and directly dropped on the glassy carbon electrode for testing.

The synthesized amino acids are characterized and quantified by hydrogen nuclear magnetic resonance (H-NMR). In H-NMR, the spectrum of H atoms on α-C in the amino acids is used as the basis for judgment. The results are shown in Figure 69. Figure 69 The H-NMR spectrum of the leucine synthesized after CoFe alloy was directly dropped on the glassy carbon electrode as a catalyst and electrolyzed for 6 hours under the potential condition of -0.7V vs. RHE.

It can be seen from Figure 69 that leucine was successfully synthesized in this embodiment; the selectivity of leucine was 9.81%, the Faradaic efficiency reached 6.00%, and the yield reached 10.22 μmol/h. Compared with the CoFe/NC carbon fiber membrane, it is obvious that the metal-loaded nitrogen-doped carbon fiber membrane material developed in the present invention has higher leucine selectivity (54.78%), Faradaic efficiency (32.26%) and yield (114.83 μmol/ h).

Amino acid synthesis device

This application also provides an amino acid synthesis device. In the description of the embodiments of this application, it is necessary It should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. indicate the orientation or positional relationship based on The orientation or positional relationship shown in the drawings is only to facilitate the description of the embodiments of the present application and simplify the description, and does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot It should be understood as a limitation on the embodiments of this application. Furthermore, the terms “first”, “second” and “third” are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.

In the description of the embodiments of this application, it should be noted that, unless otherwise clearly stated and limited, the terms "installation", "connection" and "connection" should be understood in a broad sense. For example, it can be a fixed connection or a fixed connection. Detachable connection, or integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium; it can be an internal connection between two components. For those of ordinary skill in the art, the specific meanings of the above terms in the embodiments of the present application can be understood in specific situations.

It should be understood that this application is applied in the field of electrocatalytic synthesis of amino acids. Please refer to Figure 70. Figure 70 is a schematic structural diagram of the first amino acid synthesis device in the embodiment of the present application. As shown in Figure 70, the synthesis of amino acids in Figure 70 The device includes an electrolysis reaction tank 3 and a product processing system 5; the electrolysis reaction tank 3 includes a stirring tank 3.3, a positive electrode plate 3.1, a negative electrode plate 3.1, an external circuit, a liquid feed port 3.8, a gas feed port 3.9 and a product discharge port 3.10; the outer wall of the stirring tank is provided with a liquid feed port 3.8, a gas feed port 3.9 and a product discharge port 3.10 respectively; the positive electrode plate 3.1 and the negative electrode plate 3.1 are respectively arranged inside the stirring tank 3.3; external circuit settings Outside the stirring tank 3.3, and the external circuit is connected to the positive electrode plate 3.1 and the negative electrode plate 3.1 respectively, the surface of the positive electrode plate 3.1 is coated with a catalyst for electrocatalytic synthesis of amino acids; the surface of the negative electrode plate 3.1 is coated with an electrocatalytic catalyst Catalyst for synthesizing amino acids; the catalyst is a porous carbon material catalyst doped with heteroatoms. The catalyst includes a porous carbon skeleton and heteroatoms distributed in the porous carbon skeleton. The porous carbon skeleton mainly includes nanopores, and the heteroatom elements are selected from N, O, One or more of S and P; the metal element is selected from one or more of Al, Cu, Mn, Co, Ni, Pt, Mg, and Fe. The product processing system 5 includes a centrifuge 5.1, an extraction machine 5.2 and a distillation machine 5.3; the centrifuge 5.1 is connected to the extraction machine 5.2, the centrifuge 5.1 is connected to the distillation machine 5.3, the extraction machine 5.2 is connected to the distillation machine 5.3; the product discharge port 3.10 is respectively It is connected with the inlet of centrifuge 5.1, the inlet of extraction machine 5.2 and the inlet of distillation machine 5.3; the first outlet of centrifuge 5.1, the first outlet of extraction machine 5.2 and the first outlet of distillation machine 5.3 are connected with each other to form a product processing system. Product export 5.4.

This application designs an amino acid synthesis device. The liquid raw material is introduced into the stirring tank 3.3 from the liquid feed port 3.8, the gas raw material is introduced into the stirring tank 3.3 from the gas feed port 3.9, and the external circuit controls the positive electrode plate 3.1 and the negative electrode plate. 3.1 Apply an electrocatalytic voltage to the materials in the stirring tank 3.3, and the control voltage range is between 0 and 5V; the electric stirrer of the stirring tank 3.3 stirs the materials while promoting full contact between the materials and the catalyst on the electrode plate for electrocatalytic reaction. Under the action of a catalyst for synthesizing amino acids, α-keto acid compounds are used as carbon source raw materials, nitrogen oxides are used as gaseous nitrogen source raw materials or/and liquid nitrogen source raw materials, and reactants containing amino acids are synthesized through electrocatalysis; reactants in stirred tank 3.3 Passed into the product treatment system 5, the reactant undergoes one or more operations of centrifugation, extraction and distillation, and then from the reaction High-concentration and high-value amino acid products are extracted from the reaction materials, and these amino acid products are exported from product outlet 5.4. Therefore, through the synthesis device of the present application, carbon source raw materials and nitrogen oxides can be used to perform an electrocatalytic reaction to produce amino acids.

Specifically, the stirring kettle 3.3 is an existing conventional stirring kettle, which is a large metal thick-walled kettle-shaped container with a removable cover plate on the top for installation of internal components and maintenance. In order to avoid the pressure in the stirred kettle 3.3 caused by gas generation during the reaction, the tank of the stirred kettle 3.3 must be appropriately pressure-resistant (just within the scope of the boiler pressure vessel). A leakage valve device can be designed. If the pressure exceeds 2 atmospheres, it will automatically Exhaust pressure relief, etc. The main components of the electrolysis reaction tank 3 include a positive electrode plate 3.1 and a negative electrode plate 3.1. The electrode plate is the main component in the tank. It is divided into two large-area electrode plates, positive and negative. It is coated with a catalyst for electrocatalytic synthesis of amino acids and is energized. The material is electrochemically reacted to generate the target amino acid under the condition of Stir the materials to make the tank homogeneous and promote full contact between the materials and the electrode plates to participate in the reaction; the stirring tank 3.3 is equipped with a temperature control system 3.4, which can adjust the temperature of equipment such as heating plates and water-cooled tubes. The temperature control system 3.4 can Electric heating or water cooling is used to ensure that the electrocatalytic amino acid synthesis reaction proceeds at a set temperature.

Specifically, the raw materials are introduced into the stirring tank 3.3 from the additive feeding port 3.2.

Specifically, the external circuit is an existing conventional circuit device that controls the electrode plate to output a specific voltage and current; the external circuit is used to control the positive electrode plate 3.1 and the negative electrode plate 3.1 to perform an electrocatalytic reaction on the materials in the stirring tank 3.3, and the voltage range of the electrocatalysis It is 0~5V; the electrocatalytic time is 0-48h.

Specifically, under the action of a catalyst for the specific electrocatalytic synthesis of amino acids, α-keto acids are used as carbon sources and nitrogen oxides are used as nitrogen sources, and specific amino acids are electrocatalytically synthesized in the synthesis device of the present application. These amino acids are selected from the group consisting of glycine, alanine, valine, leucine, isoleucine, methionine, proline, tryptophan, serine, tyrosine, cysteine, phenylalanine One of acid, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, histidine, selenocysteine and pyrrolysine, or Various.

Specifically, the materials of the above-mentioned positive electrode plate 3.1 and negative electrode plate 3.1 include: electrode materials with anti-oxidation and anti-corrosion properties, such as cheap graphite, activated carbon, acetylene black, organic carbon, etc., cheap metal materials such as iron, nickel, Copper, titanium, etc. and their alloys, precious metals gold, silver, platinum, palladium, iridium, etc. and their alloys are made into electrode plates in the shape of sheets or meshes. These electrode plates can withstand large currents, and the surface of the electrode plates is coated with electricity. Catalysts that catalyze the synthesis of amino acids can increase the current to improve reaction efficiency without oxidizing the catalyst.

Specifically, the α-keto acid compound solid raw material is introduced through the additive feeding port 3.2 or/and the liquid feeding port 3.8 of the synthesis device of the present application, the nitrogen oxide liquid raw material is introduced through the liquid feeding port 3.8, and the nitrogen oxide liquid raw material is introduced through the gas feeding port 3.9 The nitrogen oxide gas raw material is electrocatalytically synthesized into a specific amino acid in the synthesis device of the present application under the action of a catalyst for the specific electrocatalytic synthesis of amino acids, using α-keto acid compounds as the carbon source and nitrogen oxides as the nitrogen source.

Specifically, the α-keto acid compound is selected from the group consisting of pyruvic acid, 3-methyl-2-oxobutyric acid, and 3-methyl-2-oxypentanol. One or more of acid, 4-methyl-2-oxopentanoic acid, phenylpyruvic acid, glyoxylic acid, oxaloacetic acid, α-ketoglutaric acid and 2-butyruvic acid.

Specifically, the nitrogen oxide is selected from one or more of NO, NO ₂ , NO ₂ ^- , NO ₃ ^- , N ₂ O, NH ₃ , NH ⁴⁺ , nitrate nitrogen and nitrite nitrogen.

Specifically, the concentration of the α-keto acid compound is 10-100mM; when the nitrogen oxide is a gas, the flow rate of the nitrogen oxide is 5-50mL min ^-1 ; when the nitrogen oxide is a liquid, the concentration of the nitrogen oxide is 10-100mM. 1000mM.

Specifically, the above-mentioned nitrogen oxide gas raw material can be industrial waste gas containing nitrogen oxides or/and domestic waste gas containing nitrogen oxides, such as automobile exhaust, etc.; the above-mentioned nitrogen oxide liquid raw material can be industrial sewage containing nitrogen oxides or /And domestic sewage containing nitrogen oxides, such as livestock farm sewage, urban sewage, etc.

Specifically, not all reaction products need to undergo centrifugation, extraction, distillation, etc. One, two or three of them can be used to process the reaction products exported from the stirring tank, such as the product has a large specific gravity, colloid or suspension Products can be collected by centrifugation, some products with lower melting points can be collected by distillation, and some products are easier to separate using extraction methods.

When the above-mentioned nitrogen oxide gas raw material is industrial waste gas containing nitrogen oxides or/and domestic waste gas containing nitrogen oxides, when the above-mentioned nitrogen oxide liquid raw material can be industrial sewage containing nitrogen oxides or/and containing nitrogen oxides When using domestic sewage, the synthesis device of this application also requires a liquid material filter and a liquid material detector to pre-treat the liquid, such as preliminarily treating the liquid material, such as filter residue, etc., and then pumping it into the stirring tank to participate in the reaction; this application The synthesis device also requires gas filters, gas concentrators and gas detectors to pre-treat the gas, such as enriching the gas materials, filtering dust, etc., and then introducing them into the stirring tank to participate in the reaction.

For ease of understanding, please refer to Figure 71. Figure 71 is a schematic structural diagram of the second amino acid synthesis device in the embodiment of the present application. As shown in Figure 71, the synthesis device of the present application also includes: a liquid material filter, a liquid material detection 1, gas filter, gas concentrator, gas detector 2, sampling port 3.5, monitoring sensor 3.6, detector 3.7, temporary storage tank 7, waste treatment system 8 and control system 4. The outlet of the liquid material filter is connected to the inlet of the liquid material detector 1, and the outlet of the liquid material detector 1 is connected to the liquid feed port 3.8; the gas filter, gas concentrator and gas detector 2 are connected in sequence, and the gas detector The outlet of 2 is connected with the gas feed port 3.9. The outer wall of the stirring tank 3.3 is provided with a sampling port 3.5, the monitoring sensor 3.6 is arranged inside the stirring tank, and the detector 3.7 is connected to the liquid in the stirring tank 3.3 through the sampling port 3.5. The second outlet of the centrifuge 5.1, the second outlet of the extraction machine 5.2 and the second outlet of the distillation machine 5.3 are respectively connected with the inlet of the temporary storage tank 7, and the outlet of the temporary storage tank 7 is connected with the liquid feed port of the stirring tank 3.3. The third outlet of the centrifuge 5.1, the third outlet of the extraction machine 5.2 and the third outlet of the distillation machine 5.3 are respectively connected to the waste treatment system 8. The control system 4 is connected to the stirring tank 3.3, external circuit, liquid feed port 3.8, gas feed port 3.9, product discharge port 3.10, centrifuge 5.1, extraction machine 5.2 and distillation machine 5.3 respectively.

The synthesis device of this application also includes a collection system 6, and the product outlet 5.4 is connected to the collection system 6; Collection system 6 is used to collect the products of the high-content and high-value product processing system.

Specifically, the temporary storage tank 7 is used to temporarily store the low-component content products exported from the product processing system 5, and can be introduced into the stirring tank 3.3 again to participate in the production cycle.

Specifically, the composition and concentration of the liquid material introduced into the stirring tank 3.3 are known and do not contain impurities such as sludge. Specifically, the liquid material filter can be an existing sewage treatment device, and the liquid material detector 1 can be a liquid detector such as a mass spectrometer.

Specifically, if industrial sewage containing nitrogen oxides or/and domestic sewage containing nitrogen oxides is introduced, the sewage needs to be pretreated in advance. The pretreatment can be the existing urban sewage treatment method or factory sewage discharged into The pre-treatment device in front of the urban pipeline is carried out. The sewage treatment device includes structures such as grilles, filters, and primary sedimentation tanks to filter out coarse particles and suspended solids. Then a secondary sedimentation tank is set up. If there are many organic matter, structures such as biological ponds are needed. Remove non-settling suspended solids and degradable organic matter. Finally, set up other filter materials, rapid filter tanks and other bulk material filters according to different wastewater needs to remove other pollutants in the water and prevent the liquid entering the mixing tank 3.3 from adhering to the surface due to excessive impurities. The surface of the electrolytic plate affects the reaction efficiency. The treated sewage is passed through a liquid material detector 1 (such as mass spectrometry, etc.) to analyze the main components and concentration of the liquid material before analysis. In particular, it is necessary to measure the concentration of nitrogen oxides.

Specifically, the composition and concentration of the gas materials introduced into the mixing tank 3.3 are known. The gas materials can be provided by professional gas production companies through gas bottles, gas tanks, etc., and can be directly added to the mixing tank 3.3. Specifically, if industrial waste gas containing nitrogen oxides or/and domestic waste gas containing nitrogen oxides is introduced, these waste gases need to be pretreated in advance to remove impurities such as dust, smoke, and other environmental pollutants. The waste gas after impurity is enriched, and then passed through a gas detector (such as mass spectrometer, etc.) to analyze the main components and concentration of the gaseous materials before analysis. In particular, it is necessary to measure the concentration of nitrogen oxides.

Special work can be done to pre-treat the waste gas generated in industrial places such as factories and workshops before being discharged to the outside world, so as to meet the national waste gas discharge standards. The principles of industrial waste gas treatment include activated carbon adsorption, catalytic combustion, catalytic oxidation, acid-base neutralization, biological washing, biological trickling filtration, plasma and other principles. For example, the waste gas treatment tower adopts a five-layer waste gas adsorption, filtration and purification system. The industrial waste gas treatment design is careful, and the waste gas is purified and filtered layer by layer, and the effect is better. Scientific and innovative technologies can also be used to combine and split technologies to remove pollutants better and more efficiently. For example, the combination of low-temperature plasma technology and UV photolysis purification, the combination of rotary concentration and high-temperature plasma incineration technology remove other environmental pollutants from exhaust gas.

Specifically, the amino acid synthesis device of the present application is provided with a sampling port 3.5, which is used for sampling during the reaction process and can be divided into a manual sampling port and a dedicated sampling port for detection equipment; the sampling port 3.5 and its connected detector 3.7 can be used with the built-in The automatic control program device is connected, for example, the control system 4 is connected, and the control system 4 controls the sampling port 3.5 and its connected detector 3.7 to regularly and quantitatively sample the reaction mixture liquid in the stirring tank 3.3. The detector 3.7 can be a mass spectrometer or other instrument, Detect the components of the reactants through detector 3.7 (such as mass spectrometry, etc.), and understand the progress of the reaction in real time. You can determine whether the end point of the reaction has been reached, or whether the reactants are sufficient in real time.

Specifically, the above-mentioned monitoring sensor 3.6 can monitor the transmission of physical and chemical indicators such as thermometers and barometers. sensor.

Specifically, the high-concentration target amino acids extracted through operations such as centrifuge 5.1, extraction machine 5.2, and distillation machine 5.3 are high-content and high-value products; after processing, there is a certain target amino acid concentration, but the target amino acid concentration is low and difficult to obtain. Products with low component content that are uneconomical to extract or re-separate are products with low component content. This part of the liquid can be stored in the temporary storage tank 7 through pipelines, and then introduced into the mixing tank 3.3 again through the temporary storage tank 7; products that cannot be reused after treatment are Waste materials need to be introduced into the waste treatment system 8 for harmless treatment and then discharged. Specifically, the control system 4 is an existing conventional control device preset with a computer control program, such as a computer. The control system 4 can be used to control the stirring tank 3.3, external circuit, liquid feed port 3.8, gas feed port 3.9, and products. The system for starting and shutting down the discharge port 3.10, the centrifuge 5.1, the extraction machine 5.2 and the distillation machine 5.3. Specifically, the control system 4 controls the stirring rate of the stirring tank 3.3 and the temperature inside the stirring tank 3.3; the control system 4 controls the external circuit to The voltage and time applied by the electrode plate; the control system 4 controls the opening and closing of the liquid inlet 3.8, the gas inlet 3.9, and the product outlet 3.10; the control system 4 controls the start of the centrifuge 5.1, the extraction machine 5.2, and the distillation machine 5.3 and close.

Specifically, the control system 4 can also control the startup and shutdown of the sampling port 3.5, the temporary storage tank 7, and the waste treatment system 8.

Specifically, the control system 4 can automatically control the feeding of liquid materials, gas materials and additives, and automatically start the stirring tank 3.3. Control the external circuit to apply voltage to the electrode plate in the stirring tank 3.3. At the same time, the reaction solution in the stirring tank 3.3 is detected in real time through the sampling port 3.5 and the detector 3.7, and the changes in the concentration of materials and reactants in the stirring tank 3.3 are detected in real time; the product is automatically controlled. The discharge port 3.10 transports the product to the product processing system 5 for processing. The control system 4 controls the centrifuge 5.1, the extraction machine 5.2 and the distillation machine 5.3 to operate the product, and the centrifuge 5.1, the extraction machine 5.2 and the distillation machine 5.3 process the product. The product is transported to the collection system 6; the product with a low concentration of the target amino acid in the product treatment system 5, which is difficult to separate and extract or is uneconomical to separate, is introduced into the temporary storage tank 7, and the temporary storage tank 7 is controlled. These low-component content products are again introduced into the stirring tank 3.3 for re-electrocatalytic reaction; the control system 4 controls the opening of the waste outlet 5.5 of the product treatment system, and controls the waste materials that cannot be reused in the product treatment system 5 to be introduced into the waste treatment system 8, and controls The waste treatment system 8 conducts harmless treatment and then discharges it.

Liquid materials (such as chemical products containing nitrogen oxides, industrial waste liquids, etc.) are introduced into the stirring kettle 3.3 through the liquid feed port 3.8, and the gas materials required for the reaction (waste gas containing nitrogen oxides) are introduced into the stirring kettle through the gas feed port 3.9 3.3. Other additives (α-keto acid compounds), etc. are introduced into the stirring tank 3.3 through the additive feeding port 3.2, and the reaction in the stirring tank 3.3 is controlled by the control computer 4 and the detector 3.7. After the reaction is completed, the reacted material in the stirred tank 3.3 is pumped into the product processing system 5. Different processing methods are selected according to the composition of the material, such as centrifugation, distillation, extraction, etc., to separate the target product and introduce the high-component/high-concentration target product. In the collection system 6, low-component/low-concentration target products are introduced into the temporary storage tank 7 to participate in production recycling, and waste materials are introduced into the waste treatment system 8 for harmless treatment.

The terms "first", "second", "third", "fourth", etc. (if present) in the description of this application and the above-mentioned drawings are used to distinguish similar objects and are not necessarily used to describe specific objects. Sequence or sequence. It should be understood that data so used are interchangeable under appropriate circumstances so that the practice of the present application described herein The embodiments can, for example, be practiced in sequences other than those illustrated or described herein. Furthermore, the terms "include" and "having" and any variations thereof are intended to cover non-exclusive inclusions, e.g., a process, method, system, product, or apparatus that encompasses a series of steps or units and need not be limited to those explicitly listed. Those steps or elements may instead include other steps or elements not expressly listed or inherent to the process, method, product or apparatus.

It should be understood that in this application, "at least one (item)" refers to one or more, and "plurality" refers to two or more. "And/or" is used to describe the relationship between associated objects, indicating that there can be three relationships. For example, "A and/or B" can mean: only A exists, only B exists, and A and B exist simultaneously. , where A and B can be singular or plural. The character "/" generally indicates that the related objects are in an "or" relationship. “At least one of the following” or similar expressions thereof refers to any combination of these items, including any combination of a single item (items) or a plurality of items (items). For example, at least one of a, b or c can mean: a, b, c, "a and b", "a and c", "b and c", or "a and b and c" ”, where a, b, c can be single or multiple.

The summary of the present invention only illustrates some specific implementations of the claims, in which the technical features recorded in one or more technical solutions can be combined with any one or more technical solutions, and the technical solutions obtained by these combinations It is also within the protection scope of this application, just as if these technical solutions obtained by combination have been specifically described in the disclosure of the present invention.

Claims

A method for synthesizing organic nitrogen-containing compounds, characterized by comprising the following steps:

Under the action of a catalyst, using a carbonyl compound as a carbon source and at least one of nitrogen oxides or nitrogen hydrides as a nitrogen source, organic nitrogen-containing compounds are synthesized through electrocatalysis;

The catalyst includes porous carbon material.
The method according to claim 1, wherein the porous carbon material is a porous carbon self-supporting material;

The porous carbon material has a porosity of 0% to 99.9%;

The pore size of the porous carbon material is 0 nm to 100 nm;

The specific surface area of the porous carbon material is 10 m 2 /g ~ 4000 m 2 /g.
The method according to claim 1, wherein the catalyst further includes a support supported on the porous carbon material;

The load is selected from at least one of metal organic framework materials and metals.
The method according to claim 3, characterized in that the metal organic framework material is selected from at least one of ZIF series materials, MET series materials, MIL series materials, PCN series materials, UIO series materials, UCM series or MOF series. kind;

The metal is selected from at least one of magnesium, manganese, iron, cobalt, nickel, copper, zinc, titanium, vanadium, chromium, molybdenum, ruthenium, rhodium, palladium, silver, bismuth, zirconium, and cerium.
The method of claim 1, wherein the catalyst is selected from at least one of carbon fiber cloth, ZIF-8 supported polyacrylonitrile membrane, and CoFe alloy supported nitrogen-doped carbon fiber membrane.
The method of claim 1, wherein the carbonyl compound is selected from the group consisting of aldehydes, ketones, carboxylic acids, diketones, ketoacids, aminoketones, and hydroxyketones. At least one of compounds or ketone ether compounds;

The nitrogen oxide is selected from at least one of NO 2 , NO, N 2 O, N 2 O 3 , N 2 O 4 , NO 3 - and NO 2 - ;

The nitrogen hydride is selected from at least one of NH 2 OH, NH 3 and NH 4 + .
The method according to claim 1, characterized in that the concentration of the carbon source is above 0.1 mmol/L.
The method according to claim 1, wherein the nitrogen source is a gas, and the flow rate of the nitrogen source is 1 sccm or more;

Alternatively, the nitrogen source is liquid, and the concentration of the nitrogen source is 0.001 mol/L to 100 mol/L.
The method according to claim 1, characterized in that the voltage of the electrocatalysis is 5V vs. RHE ~ -5V vs. RHE.
The method according to claim 1, characterized in that the organic nitrogen-containing compound is selected from at least one of oxime, amine, nitrile and amino acid.
A method for synthesizing amino acid nitrogen-containing organic matter, which is characterized in that it includes the following steps:

Under the action of a porous carbon material catalyst, alpha-keto acid carbonyl compounds are used as the carbon source, and at least one of nitrogen oxides or nitrogen hydrides is used as the nitrogen source, and organic nitrogen compounds are synthesized through electrocatalysis.
The synthesis method according to claim 11, characterized in that the total pore volume of the porous carbon material catalyst is 0.05-5.0 cm 3 /g, and the specific surface area is greater than 100-4000 m 2 /g.
The synthetic method according to claim 11, characterized in that the α-keto acid compounds include pyruvic acid, 4-hydroxyphenylpyruvic acid, 3-hydroxypyruvic acid, 3-thiopyruvic acid, 3-methyl -2-Oxobutyric acid, 3-indolepyruvate, imidazole-4-pyruvate, 2-butyruvic acid, 6-amino-2-oxohexanoic acid, 4-(methylthio)-2-oxo -Butyric acid, 3-hydroxy-2-oxo-butyric acid, 4-amino-2,4-dioxobutyric acid, 5-amino-2,5-dioxopentanoic acid, 5-[diaminobutyric acid Methyl]amino]-2-oxopentanoic acid, 3-methyl-2-oxopentanoic acid, 4-methyl-2-oxopentanoic acid, phenylpyruvic acid, glyoxylic acid, oxaloacetic acid, α- One or more of ketoglutaric acid and 2-butyric acid.
The synthesis method according to claim 11, characterized in that the nitrogen oxides are selected from NO, NO2 , NO2- , NO3- , N2O , NH3 , NH4 + , NH2OH , nitric acid One or more of salt nitrogen and nitrite nitrogen.
The synthesis method according to claim 11, characterized in that the concentration of the α-keto acid compound is greater than or equal to 5mM.
The synthesis method according to claim 11, characterized in that when the nitrogen oxide is a gas, the flow rate of the nitrogen oxide is greater than or equal to 10 mL min -1 .
The synthesis method according to claim 11, characterized in that when the nitrogen oxide is liquid, the concentration of the nitrogen oxide is greater than or equal to 5mM.
The synthesis method according to claim 11, characterized in that the voltage range of the electrocatalysis is -0.1V vs. RHE to -5V vs. RHE.
The synthetic method according to claim 11, wherein the organic nitrogen compound includes one or more of amino acids, organic oximes, organic amines and amides;

The amino acids are glycine, alanine, valine, leucine, isoleucine, methionine, proline, tryptophan, serine, tyrosine, cysteine, and phenylalanine One of acid, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, histidine, selenocysteine and pyrrolysine, or Various.
The synthesis method according to claim 11, wherein the porous carbon material catalyst includes a porous carbon skeleton and heteroatoms or/and multi-metal atoms distributed in the porous carbon skeleton, and the porous carbon skeleton mainly includes Microporous, mesoporous and macroporous carbon structural materials, the heteroatoms are selected from one or more of N, O, S and P, and the multi-element metal atoms are selected from Al, Cu, Mn, Co, Ni, One or more of Mg, Fe, Zn, Pt, Pd, Ag, Au and Ru.
A method for producing amino acids from nitrogen oxide exhaust gas and wastewater is characterized by including:

Mix nitrogen source, alpha-keto acid compound and porous carbon material catalyst in an electrolytic cell, and after electrochemical reaction, amino acids are obtained;

The nitrogen source consists of waste gas containing nitrogen oxides or/and wastewater containing nitrogen oxides.
The method of claim 21, wherein the exhaust gas containing nitrogen oxides includes one or more of NO, NO2 and N2O .
The method of claim 21, wherein the wastewater containing nitrogen oxides includes one or more of ammonia nitrogen, nitrate nitrogen and nitrite nitrogen.
The method according to claim 21, wherein the amino acids include glycine, alanine, valine, leucine, isoleucine, methionine, proline, tryptophan, serine , tyrosine, cysteine, phenylalanine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, histidine, selenium One or more of cystine and pyrrolysine.
The method according to claim 21, characterized in that the concentration of the α-keto acid compound is greater than or equal to 5mM; the flow rate of the exhaust gas containing nitrogen oxides is greater than or equal to 10mL min -1 ; The concentration of wastewater is greater than or equal to 5mM.
The method according to claim 21, characterized in that the electrochemical reaction includes a two-electrode electrochemical reaction system or a three-electrode electrochemical reaction system;

The two-electrode electrochemical reaction system includes an anode, a cathode, a separator and an electrolyte;

The three-electrode electrochemical reaction system includes a counter electrode, a working electrode, a reference electrode, a separator and an electrolyte.
The method according to claim 26, wherein the material of the anode includes one or more of platinum carbon catalyst, ruthenium carbon and palladium carbon;

The material of the cathode includes a cathode made of the porous carbon material catalyst or/and a cathode coated with the porous carbon material catalyst;

The membrane includes a proton exchange membrane;

The electrolyte includes an acidic aqueous solution, an alpha-keto acid compound and the nitrogen source;

The acidic aqueous solution is selected from one or more of phosphate buffered saline solution, H 2 SO 4 , HCl, Na 2 SO 4 , NaNO 3 and NaNO 2 .
The method according to claim 26, characterized in that:

The working electrode includes a working electrode made of the porous carbon material catalyst or/and a working electrode coated with the porous carbon material catalyst;

The counter electrode includes one or more of a graphite carbon electrode, a platinum electrode, a platinum carbon electrode, and a platinum mesh electrode;

The reference electrode includes a silver/silver chloride reference electrode or a mercury/mercury oxide reference electrode;

The membrane includes a proton exchange membrane;

The electrolyte includes an acidic aqueous solution, an alpha-keto acid compound and the nitrogen source;

The acidic aqueous solution is selected from one or more of phosphate buffered saline solution, H 2 SO 4 , HCl, Na 2 SO 4 , NaNO 3 and NaNO 2 .
The method according to claim 26, characterized in that the potential range of the three-electrode electrochemical reaction system is -0.1~-5V vs. RHE;

The potential range of the two-electrode electrochemical reaction system is -0.1~-5V.
The method for synthesizing amino acids is characterized by comprising the following steps:

Under the action of a catalyst, α-keto acids are used as amino acid precursors and nitrogen oxides are used as nitrogen sources to synthesize amino acids through electrocatalysis;

The catalyst includes a porous carbon self-supporting material and a metal supported on the porous carbon self-supporting material.
The method according to claim 30, characterized in that the pore volume of the porous carbon self-supporting material is 0.01cm 3 g -1 ~ 10.0cm 3 g -1 ;

The pore size of the porous carbon self-supporting material is 0.5nm to 100nm;

The specific surface area of the porous carbon self-supporting material is 10m 2 g -1 to 3000m 2 g -1 .
The method according to claim 30, wherein the metal is selected from at least one of manganese, iron, cobalt, nickel, copper, zinc, titanium, vanadium, chromium, molybdenum, ruthenium, rhodium, palladium, platinum and silver. A sort of.
The method of claim 30, wherein the catalyst further includes non-metallic elements doped in the porous carbon self-supporting material;

The non-metal element is selected from at least one of N, O, F, B, P and S.
The method according to claim 32 or 33, characterized in that the catalyst includes CoFe alloy supported N-doped carbon fiber membrane, NiFe alloy supported N-doped carbon fiber membrane, Fe-supported N-doped carbon fiber membrane, Co-loaded N-doped carbon fiber membrane, Ni-loaded N-doped carbon fiber membrane, Mn-loaded N-doped carbon fiber membrane, Cu-loaded N-doped carbon fiber membrane, Zn-loaded N-doped carbon fiber membrane, Ti-loaded N-doped carbon fiber membrane, V-loaded N-doped carbon fiber membrane, Cr-loaded N-doped carbon fiber membrane, Mo-loaded N-doped carbon fiber membrane, Ru-loaded N-doped carbon fiber membrane, Rh-loaded N-doped carbon fiber membrane, Pd-loaded At least one of an N-doped carbon fiber film, a Pt-loaded N-doped carbon fiber film, and an Ag-loaded N-doped carbon fiber film.
The method according to claim 30, characterized in that the α-keto acid compound is selected from the group consisting of pyruvic acid, 4-hydroxyphenylpyruvic acid, 3-hydroxypyruvic acid, 3-thiopyruvic acid, 3-methyl -2-oxobutyric acid, 3-indolepyruvate, imidazole-4-pyruvate, 6-amino-2-oxohexanoic acid, 4-(methylthio)-2-oxo-butyric acid, 3 -Hydroxy-2-oxo-butyric acid, 4-amino-2,4-dioxobutyric acid, 5-amino-2,5-dioxopentanoic acid, δ-guanidino-α-ketovaleric acid , 3-methyl-2-oxyvaleric acid, 3-methyl-2-oxybutyric acid, 4-methyl-2-oxopentanoic acid, phenylpyruvic acid, glyoxylic acid, oxaloacetic acid, α- Ketoglutaric acid, 2-butyric acid, 2-pentanoic acid, 2-oxohexanoic acid, 2-cyclobutyl-2-carbonylacetic acid, 2-oxy-4-phenylbutyric acid, and benzoyl at least one of formic acid;

The nitrogen oxide is selected from at least one of NO, NO 2 , NO 2 - , NO 3 - , N 2 O, NH 2 OH, and NH 3 .
The method according to claim 30, characterized in that the voltage of the electrocatalysis is -5V vs. RHE ~ 5V vs. RHE.
The method of claim 30, wherein the concentration of the amino acid precursor is 5 mmol/L to 10 mol/L.
The method of claim 30, wherein the nitrogen source is a gas, and the flow rate of the nitrogen source is 5 mL/min or more;

Alternatively, the nitrogen source is liquid, and the concentration of the nitrogen source is 5 mmol/L to 2000 mmol/L.
The method according to claim 30, wherein the amino acid is leucine, isoleucine, valine, alanine, glutamic acid, aspartic acid, glycine, 2-aminobutyric acid , at least one of 2-aminovaleric acid, 2-aminocaproic acid, 2-amino-cyclobutylacetic acid, homophenylalanine, and phenylglycine.
An amino acid synthesis device, characterized in that it includes:

Electrolysis reaction tanks and product handling systems;

The electrolysis reaction tank includes a stirring tank, a positive electrode plate, a negative electrode plate, an external circuit, a liquid feed port, a gas feed port and a product discharge port;

The outer wall of the stirring tank is respectively provided with a liquid feed port, a gas feed port and a product discharge port;

The positive electrode plate and the negative electrode plate are respectively arranged inside the stirring tank; the external circuit is arranged outside the stirring tank, and the external circuit is connected to the positive electrode plate and the negative electrode respectively. The electrode plates are connected, the surface of the positive electrode plate is coated with a commercial metal carbon catalyst; the surface of the negative electrode plate is coated with a porous carbon material catalyst;

The product treatment system includes a centrifuge, an extraction machine and a distillation machine; the centrifuge is connected to the extraction machine, the centrifuge is connected to the distillation machine, the extraction machine is connected to the distillation machine; the The product discharge port is respectively connected with the inlet of the centrifuge, the inlet of the extraction machine and the inlet of the distillation machine; the first outlet of the centrifuge, the first outlet of the extraction machine and the distillation machine The first outlets are interconnected to form a product outlet of the product processing system.
The synthesis device according to claim 40, further comprising a liquid material filter and a liquid material detector, the outlet of the liquid material filter is connected to the inlet of the liquid material detector, and the liquid material detector The outlet of the device is connected with the liquid feed port.
The synthesis device according to claim 40, further comprising a gas filter, a gas concentrator and a gas detector, the gas filter, the gas concentrator and the gas detector being connected in sequence, The outlet of the gas detector is connected with the gas feed port.
The synthesis device according to claim 40, wherein the electrolysis reaction tank further includes: a sampling port, a monitoring sensor and a detector;

A sampling port is provided on the outer wall of the stirring tank, the monitoring sensor is arranged inside the stirring tank, and the detector is connected to the liquid in the stirring tank through the sampling port.
The synthesis device according to claim 40, further comprising a temporary storage tank, the second outlet of the centrifuge, the second outlet of the extraction machine and the second outlet of the distillation machine are respectively connected with the second outlet of the centrifuge. The inlet of the temporary storage tank is connected, and the outlet of the temporary storage tank is connected with the liquid feed port of the stirring tank.
The synthesis device according to claim 40, further comprising a waste treatment system, the third outlet of the centrifuge, the third outlet of the extraction machine and the third outlet of the distillation machine are respectively connected with the Waste disposal system connections.
The synthesis device according to claim 40, further comprising a control system, the control system is respectively connected with the stirring tank, the external circuit, the liquid feed port, the gas The feed port, the product discharge port, the centrifuge, the extraction machine and the distillation machine are connected.