CN116082130B - Process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver - Google Patents

Process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver Download PDF

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CN116082130B
CN116082130B CN202310054627.4A CN202310054627A CN116082130B CN 116082130 B CN116082130 B CN 116082130B CN 202310054627 A CN202310054627 A CN 202310054627A CN 116082130 B CN116082130 B CN 116082130B
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glyoxal
composite silver
ethylene glycol
doped graphene
reaction
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CN116082130A (en
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钟加群
钟明强
李兰清
陈耕宏
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Hangzhou Fuyang Yongxing Chemical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation

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Abstract

The application relates to the technical field of chemistry and chemical engineering, and particularly discloses a process for producing glyoxal by catalytic oxidation of ethylene glycol by using composite silver. A process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver comprises the following steps: 3-5 layers of composite silver catalyst are placed in a reaction section of a catalytic reactor; feeding vaporized glycol, washed air and water vapor into a reactor at the reaction temperature of 300-600 ℃ for oxidation reaction to generate glyoxal product; the composite silver catalyst in the S1 is prepared by taking N-doped graphene as a carrier and loading Co and Ag nano particles; the S2 oxidation reaction is carried out in the presence of nitrogen, and the molar ratio of the nitrogen to the glycol is controlled to be (40-50): 1, a step of; the molar ratio of oxygen to glycol in the air is controlled to be (1.25-1.35): 1, a step of; glycol on catalystIs 6-50hr ‑1 . The catalyst has the effect of improving the catalytic activity.

Description

Process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver
Technical Field
The application relates to the technical field of chemistry and chemical engineering, in particular to a process for producing glyoxal by catalytic oxidation of ethylene glycol by using composite silver.
Background
Glyoxal, also known as oxalic aldehyde, is the aliphatic dialdehyde with the simplest molecular structure. The glyoxal molecule contains 2 carbonyl groups which are connected with each other, so that the glyoxal molecule has special chemical properties except the universality of fatty aldehyde, can be subjected to addition or condensation reaction with alcohol, amine, amide, aldehyde, hydroxyl-containing compounds and the like, and can also be subjected to cross-linking reaction with protein-like animal glue, cellulose, polyvinyl alcohol, urea and the like, and therefore, the glyoxal molecule has wide application in the aspects of textile printing and dyeing, medicines, coatings, light industry, environmental protection and the like, and has wide development and utilization prospects.
The products sold in the market at present are 30% -40% glyoxal aqueous solution, and the products contain more impurities, mainly formaldehyde and hydroxy acetaldehyde which are side reaction products in the glycol reaction stage, so that the selectivity of the reaction stage needs to be improved. In the related art, it is proposed that the electrolytic silver catalyst is used for catalyzing the reaction of ethylene glycol and air to produce glyoxal, but the service life of the electrolytic silver catalyst is shorter in the use process, and the activity and selectivity of the electrolytic silver catalyst are reduced due to the high Wen Yishao knot, so that the glyoxal production process is adversely affected.
Disclosure of Invention
In order to keep higher catalytic activity and product yield, the application provides a process for producing glyoxal by catalytic oxidation of ethylene glycol by using composite silver.
The application provides a technical scheme which adopts the following steps:
a process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver comprises the following steps:
s1, filling a composite silver catalyst into a reaction section of a catalytic reactor in 3-5 layers;
s2, at the reaction temperature of 300-600 ℃, ethylene glycol is vaporized and then is sent into a reactor together with air and water vapor for oxidation reaction, so as to generate glyoxal products;
the composite silver catalyst in the S1 is prepared by taking N-doped graphene as a carrier and loading Co and Ag nano particles;
the S2 oxidation reaction is carried out in the presence of nitrogen, and the molar ratio of the nitrogen to the glycol is controlled to be (40-50): 1, a step of;
the molar ratio of oxygen to glycol in the air is controlled to be (1.25-1.35): 1, a step of;
the liquid hourly space velocity of ethylene glycol on the catalyst is 6-50hr -1 。
Through adopting above-mentioned scheme, the compound silver catalyst that this application adopted uses N doped graphene as the carrier, through the incorporation of nitrogen element in the graphite alkene production N-C bond, wherein the C atom adjacent to the N atom will have more positive charge, can effectively strengthen the electronegativity of graphite alkene material, owing to there is a large amount of nitrogen structures between Ag nanoparticle and the N doped graphene carrier, therefore have very high binding energy, can evenly disperse and fix Ag nanoparticle on graphite alkene carrier surface, the dispersity of nano silver particle is good, can improve its sintering resistance, thereby improve the stability of catalyst, and the reinforcing of electron adsorptivity can create better catalytic condition for oxidation reduction reaction, simultaneously graphite alkene material has fabulous heat conduction performance, can improve reaction efficiency. The existence of the carrier can improve the metal surface area, the contact area of the Ag nano particles and the gas is larger, the catalytic active sites are more, and the Co nano particles can improve the catalytic activity of the ethylene glycol catalytic oxidation reaction.
The supported composite silver catalyst has longer catalytic life, can reduce the reaction temperature of the reaction of generating the glyoxal by the glycol to a certain extent, avoids the sintering phenomenon of the catalyst under the condition of high temperature, limits the feeding parameters of the reaction in the production process adopted by the application, controls the molar ratio of nitrogen to the glycol, oxygen to the glycol in the air and the liquid hourly space velocity of the glycol in a certain proper range, and can ensure that the catalytic oxidation effect is better.
Preferably, the composite silver catalyst is prepared by the following steps:
fully dissolving 1-2 parts of N-doped graphene and 0.1-0.2 part of cobalt nitrate hexahydrate in a DMF solution at 90-100 ℃ and uniformly stirring, drying the obtained mixture, and then pyrolyzing the dried mixture at 850-900 ℃ for 1-2 hours in a nitrogen atmosphere to obtain the N-doped graphene loaded with Co nano particles;
step two, agN0 with the mass concentration of 1 to 5 percent 3 The solution is electrolyte, the N-doped graphene treated in the first step is taken as a cathode of an electrolytic reaction, silver blocks are taken as an anode of the electrolytic reaction, and the current density is 15-20A dm -2 And (3) the temperature of the electrolyte is 50-60 ℃, the electrolysis time is 1-2min, then the cathode N-doped graphene is washed by deionized water, and the cathode N-doped graphene is placed in an air atmosphere at 400-600 ℃ for roasting for 2-3h, so that the composite silver catalyst is prepared.
By adopting the scheme, the specific mode steps of loading the Co and Ag nano particles on the N-doped graphene are limited, the Co nano particles are firstly loaded on the N-doped graphene by a direct pyrolysis method to occupy certain adsorption sites, so that the subsequently loaded nano silver particles on the carrier can be more dispersed, and sintering is difficult to occur. The nitrogen modification of the graphene material can change the electronic structure of the carbon surface and improve the conductivity, so that the Ag can be chemically modified + Reducing to disperse Ag nano particles on the N-doped graphene carrier, and reducing aggregation of the generated silver particles, so that good catalytic activity of the silver particles can be maintained. By adopting the mode, the composite silver catalyst with longer service life and good catalytic performance can be prepared.
Preferably, in the composite silver catalyst, the nitrogen content of the N-doped graphene is 3-5wt%.
Through adopting above-mentioned scheme, when the nitrogen content of N doped graphene is in this within range, the modification effect to graphene material itself is better, and the carrier is better to the adsorptivity of Ag nanoparticle, and can provide certain catalytic activity, has better auxiliary effect to silver catalyst catalytic oxidation ethylene glycol production glyoxal.
Preferably, the N-doped graphene is pretreated by:
adding 1-2 parts of N-doped graphene into 50-100ml of water, stirring, adding 10-15 parts of potassium hydroxide and 8-10 parts of white phosphorus, uniformly mixing, performing ultrasonic treatment on the mixture for 30-40min, performing hydrothermal treatment at 160-180 ℃ for 5 days, cooling, filtering, washing with deionized water, performing vacuum drying treatment at 80-90 ℃ for 10-12h, and finally performing treatment on the product at 500-600 ℃ for 6-8h under the atmosphere of high-purity helium.
By adopting the scheme, the N-doped graphene is pretreated, and phosphorus is doped in the N-doped graphene by a hydrothermal treatment method, so that the deep oxidation reaction of ethylene glycol can be inhibited, the generation of side reaction products is reduced, the selectivity of the ethylene glycol for producing glyoxal products is improved, and the subsequent treatment workload of the obtained glyoxal products is reduced.
Preferably, the loading amount of the N-doped graphene loaded Co nano-particles is 1-20mg/g, and the loading amount of the loaded Ag nano-particles is 10-100mg/g.
By adopting the scheme, the Co nano particles and the Ag nano particles loaded on the N-doped graphene carrier can have a good catalytic effect within the loading range, and the catalytic oxidation reaction can be ensured to be carried out under the condition of low-dosage active components, so that the good catalytic effect can be achieved.
Preferably, the size distribution of the Ag nano-particles is 2-5nm.
By adopting the scheme, the particle size of the Ag nano particles is controlled within the range, so that the combination of the Ag nano particles and the carrier is better, the surface area of the silver particles is larger, and the catalytic activity is better.
Preferably, the glyoxal product is subjected to the following purification treatments:
step one, spraying the glyoxal product generated in the step 2 by adopting water to obtain glyoxal crude product solution;
step two, purifying glyoxal by taking a mixed solvent of isooctanol, isohexanol and isosunflower alcohol as a purifying agent and xylene as a diluting agent, wherein the extraction time is 10-15min.
Through adopting above-mentioned scheme, isooctanol, isohexanol, isosunflower alcohol are superior to formaldehyde and glyoxal's separation effect, extract through the three mixture, can improve extraction efficiency, and extraction effect is good, and in addition xylene is as the diluent, carries out purification treatment to glyoxal product that glycol oxidation reaction obtained, can make the product higher quality.
Preferably, in the second step, the volume ratio of isooctanol, isohexanol and isosunflower alcohol is (50-60): 15-20: (25-30).
By adopting the scheme, when the volume ratio of the three is the numerical value in the range, the synergistic extraction effect is better.
In summary, the present application has the following beneficial effects:
1. according to the preparation method, the N-doped graphene is used as a carrier, the composite silver catalyst prepared by loading the Ag nano particles and the Co nano particles is used for catalyzing and oxidizing ethylene glycol to produce glyoxal, good catalytic stability and catalytic activity can be kept in the use process, the feeding parameters and the reaction temperature of the reaction are adjusted, good catalytic effect can be achieved, and the product yield is high.
2. The composite silver catalyst prepared by the method has good heat conduction performance by taking the N-doped graphene as a carrier, can improve the reaction efficiency, loads Ag nano particles on the carrier by an electrolytic method, and improves the catalytic activity of the silver particles by assistance of Co nano particles, so that the advantages of the loaded silver catalyst and the electrolytic silver catalyst can be combined, the service life of the catalyst is prolonged, the reaction temperature can be reduced to a certain extent, the high-temperature sintering phenomenon of the catalyst is not easy to occur, and the higher catalytic activity and selectivity are ensured.
Detailed Description
The present application is described in further detail below in connection with preparation examples, examples and comparative examples.
Preparation example
Preparation example 1: preparation of composite silver catalyst
Fully dissolving 2g N doped graphene (BKMK 2006) and 0.02g of cobalt nitrate hexahydrate in a DMF solution at 100 ℃, uniformly stirring, drying the obtained mixture, and then pyrolyzing the dried mixture at 900 ℃ for 1.5 hours in a nitrogen atmosphere to obtain N doped graphene loaded with Co nano particles;
step two, agN0 with mass concentration of 5% 3 The solution is electrolyte, the N-doped graphene treated in the first step is taken as a cathode of an electrolytic reaction, a silver block is taken as an anode of the electrolytic reaction, and the current density is 16A dm -2 The temperature of the electrolyte is 55 ℃, and the electrolysis time isAnd (3) after 1min, cleaning the cathode N-doped graphene by deionized water, and roasting for 2h in an air atmosphere at 400 ℃ to obtain the composite silver catalyst. Wherein the loading capacity of the N-doped graphene loaded Co nano-particles is 20mg/g, and the loading capacity of the loaded Ag nano-particles is 50mg/g.
Preparation example 2:
the composite silver catalyst prepared in the preparation example is different from the preparation example 1 in that the adopted N-doped graphene is subjected to the following pretreatment:
adding 2g N doped graphene powder into water, stirring, adding 36g of potassium hydroxide and 20g of white phosphorus, uniformly mixing, performing ultrasonic treatment on the mixture for 30min, performing hydrothermal treatment at 180 ℃ for 5 days, cooling, filtering, washing with deionized water, performing vacuum drying at 80 ℃ for 12h, and finally performing treatment on the product at 600 ℃ for 6h under the atmosphere of high-purity helium.
Preparation example 3:
the composite silver catalyst prepared in the preparation example is different from the preparation example 2 in that the loading capacity of the N-doped graphene loaded Co nano particles in the composite silver catalyst is 8mg/g, and the loading capacity of the loaded Ag nano particles is 92mg/g.
Examples
Example 1:
a process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver comprises the following steps:
s1, presetting a catalyst: 2g of the composite silver catalyst prepared in preparation example 1 is taken and is filled in the reaction section of a catalytic reactor in 4 layers, and the thickness of each layer of catalyst is 20mm.
S2, catalytic oxidation reaction: in the presence of nitrogen, the glycol aqueous solution is pumped into a gasifier by a metering pump for vaporization, and then is sent into a reactor together with air and water vapor. The liquid hourly space velocity of ethylene glycol is 50hr -1 The molar ratio of oxygen to glycol in the air is controlled to be 1.31, the molar ratio of nitrogen to glycol is controlled to be 50, the molar ratio of water to oxygen is 5, and oxidation reaction is carried out at the reaction temperature of 300 ℃ to generate glyoxal products.
S3, purifying the product:
quenching the generated glyoxal product, spraying and absorbing, and controlling the water supplementing amount of spraying to obtain 40% glyoxal crude product solution;
step two, using a mixed solvent of isooctyl alcohol, trioctylamine and tributyl phosphate as a purifying agent, wherein the volume ratio of the isooctyl alcohol to the trioctylamine to the tributyl phosphate is 50:20:30, purifying glyoxal by using dimethylbenzene as a diluent, wherein the extraction time is 15min.
Example 2:
the process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver is different from that of example 1 in that the reaction temperature is 600 ℃.
Example 3:
the process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver is different from example 1 in that the reaction temperature is 410 ℃.
Example 4:
the process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver is different from example 3 in that the composite silver catalyst prepared in preparation example 2 is adopted.
Example 5:
the process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver is different from example 4 in that the composite silver catalyst prepared in preparation example 3 is used.
Comparative example
Comparative example 1: the process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver differs from example 1 in that the ethylene glycol oxidation reaction is catalyzed with a commercially available electrolytic silver catalyst.
Comparative example 2: the process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver is different from that of example 1 in that isooctyl alcohol is used as a purifying agent for purification treatment.
Detection result
The results of the product measurements for examples 1-5 and comparative examples 1-2 are shown in Table 1.
TABLE 1 results of product measurements for examples 1-5 and comparative examples 1-2
As can be seen from the experimental data in Table 1, the composite silver catalyst of examples 1-5 was used in combination with the production process to produce glyoxal, the conversion rate of raw material ethylene glycol was between 99.1% and 100%, the selectivity of glyoxal in the raw material alcohol product was between 86.5% and 88.2%, and the conversion rate of raw material of comparative example 1-2 was between 89.2% and 99.1%, and the selectivity of glyoxal in the raw material alcohol product was between 75.3% and 86.5%, so that the catalytic activity and selectivity of the composite silver catalyst used in the present application were high, and the production process of glyoxal was better. The catalysts used in examples 1 to 5 had a service life of 120 to 150 days, whereas the catalyst used in comparative example 1 had a service life of 60 days, in contrast to the longer service life of the composite silver catalyst prepared in the present application. As can be seen from comparative examples 1-5 and comparative example 2, after the purification treatment of the present application, the mass fraction of formaldehyde in the glyoxal product was successfully reduced to less than 0.5%, so that the quality of the glyoxal product was improved.
Comparative example 1 and comparative example 1 show that the composite silver catalyst used in the present application has better catalytic activity at the same reaction temperature. The composite silver catalyst takes N-doped graphene as a carrier, has good heat conduction performance, can improve reaction efficiency, simultaneously loads Ag nano particles by a chemical electrolysis method, uniformly disperses the Ag particles by the action of the carrier, improves the surface area of the Ag particles, and ensures better reaction catalytic activity by the existence of Co nano particles. Meanwhile, the N-doped graphene is doped with phosphorus element, so that the deep oxidation reaction of ethylene glycol can be inhibited, the generation of side reaction products is reduced, and the selectivity of the ethylene glycol for producing glyoxal products is improved. The composite silver catalyst prepared by the method is a supported silver catalyst, the reaction temperature of the reaction for generating glyoxal from ethylene glycol can be reduced to a certain extent, the phenomenon that the catalyst is easy to sinter at high temperature is avoided, and the catalyst has longer catalytic life. As can be seen from comparative examples 1 and 2, the mixed solvent of isooctanol, isohexide and isosunflower alcohol is used as a purifying agent, and xylene is used as a diluting agent to purify the glyoxal crude product, wherein isooctanol, isohexide and isosunflower alcohol are all C5-C10 alcohols, the separation effect of formaldehyde and glyoxal is better, and the mixed solvent is adopted for extraction, so that compared with the single extracting agent, the extraction efficiency of the mixed solvent is obviously improved, and the extraction effect is better.
As can be seen from comparative example 1 and examples 2-3, the catalytic oxidation of ethylene glycol using the composite silver catalyst is preferably carried out at a reaction temperature of 410 ℃. Although the selectivity of glyoxal generated by the reaction is improved when the reaction temperature is 600 ℃, the increase amplitude is slightly small, and compared with the catalyst, the service life of the catalyst can be prolonged by the reduction of the reaction temperature, so that the catalyst is catalyzed by the composite silver catalyst at the reaction temperature of 410 ℃ under the measurement. As can be seen from comparative examples 3 and 4, the N-doped graphene material is preferably pretreated, and phosphorus is doped therein, so that the deep oxidation reaction of ethylene glycol is inhibited by the action of phosphorus, and the generation of byproducts is reduced, thereby improving the selectivity of glyoxal product. In comparative example 4 and example 5, the loading amount of the Co nanoparticles supported by the N-doped graphene is preferably 8mg/g, and the loading amount of the Ag nanoparticles supported by the N-doped graphene is 92mg/g, so that the composite silver catalyst can play a good catalytic role.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.

Claims (7)

1. A process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver is characterized by comprising the following steps:
s1, filling a composite silver catalyst into a reaction section of a catalytic reactor in 3-5 layers;
s2, at the reaction temperature of 300-600 ℃, ethylene glycol is vaporized and then is sent into a reactor together with air and water vapor for oxidation reaction, so as to generate glyoxal products;
the composite silver catalyst in the S1 is prepared by taking N-doped graphene as a carrier and loading Co and Ag nano particles;
the S2 oxidation reaction is carried out in the presence of nitrogen, and the molar ratio of the nitrogen to the glycol is controlled to be (40-50): 1, a step of;
the molar ratio of oxygen to glycol in the air is controlled to be (1.25-1.35): 1, a step of;
the liquid hourly space velocity of ethylene glycol on the catalyst is 6-50hr -1 ；
The composite silver catalyst is prepared by the following steps:
fully dissolving 1-2 parts of N-doped graphene and 0.1-0.2 part of cobalt nitrate hexahydrate in a DMF solution at 90-100 ℃ and uniformly stirring, drying the obtained mixture, and then pyrolyzing the dried mixture at 850-900 ℃ for 1-2 hours in a nitrogen atmosphere to obtain the N-doped graphene loaded with Co nano particles;
step two, agNO with the mass concentration of 1 to 5 percent 3 The solution is electrolyte, the N-doped graphene treated in the first step is taken as a cathode of an electrolytic reaction, silver blocks are taken as an anode of the electrolytic reaction, and the current density is 15-20A dm -2 And (3) the temperature of the electrolyte is 50-60 ℃, the electrolysis time is 1-2min, then the cathode N-doped graphene is washed by deionized water, and the cathode N-doped graphene is placed in an air atmosphere at 400-600 ℃ for roasting for 2-3h, so that the composite silver catalyst is prepared.
2. The process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver according to claim 1, wherein the nitrogen content of the N-doped graphene in the composite silver catalyst is 3-5wt%.
3. The process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver according to claim 2, wherein the N-doped graphene is pretreated by:
adding 1-2 parts of N-doped graphene into 50-100ml of water, stirring, adding 10-15 parts of potassium hydroxide and 8-10 parts of white phosphorus, uniformly mixing, performing ultrasonic treatment on the mixture for 30-40min, performing hydrothermal treatment at 160-180 ℃ for 5 days, cooling, filtering, washing with deionized water, performing vacuum drying treatment at 80-90 ℃ for 10-12h, and finally performing treatment on the product at 500-600 ℃ for 6-8h under the atmosphere of high-purity helium.
4. The process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver according to claim 3, wherein the loading amount of the N-doped graphene loaded Co nanoparticles is 1-20mg/g, and the loading amount of the loaded Ag nanoparticles is 10-100mg/g.
5. The process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver according to claim 4, wherein the size distribution of Ag nanoparticles is 2-5nm.
6. The process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver according to claim 1, wherein said glyoxal product is purified by:
step one, spraying the glyoxal product generated in the step 2 by adopting water to obtain glyoxal crude product solution;
step two, purifying glyoxal by taking a mixed solvent of isooctanol, isohexanol and isosunflower alcohol as a purifying agent and xylene as a diluting agent, wherein the extraction time is 10-15min.
7. The process for producing glyoxal by catalytic oxidation of ethylene glycol with composite silver according to claim 6, wherein in the second step, the volume ratio of isooctanol, isohexanol and isosunflower alcohol is (50-60): (15-20): (25-30).
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CN103772169A (en) * 2014-02-12 2014-05-07 复旦大学 Method for synthesizing low-impurity content glyoxal through gas phase oxidation
CN105457647A (en) * 2015-12-10 2016-04-06 复旦大学 Nano-perovskite-type catalyst La(1-X)BixCoO3 as well as preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
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