CN112778118B - Method for preparing glyoxylic acid from methyl glycolate - Google Patents
Method for preparing glyoxylic acid from methyl glycolate Download PDFInfo
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- CN112778118B CN112778118B CN201911069312.7A CN201911069312A CN112778118B CN 112778118 B CN112778118 B CN 112778118B CN 201911069312 A CN201911069312 A CN 201911069312A CN 112778118 B CN112778118 B CN 112778118B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/373—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in doubly bound form
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The application discloses a method for preparing glyoxylic acid from methyl glycolate. The method comprises the following steps: contacting a material containing methyl glycolate and a mixed solvent with an oxidation catalyst and a hydrolysis catalyst in the presence of an oxygen source to react to obtain glyoxylic acid; wherein, air and/or oxygen is used as an oxygen source; obtaining the oxidation catalyst by loading a metal on a nitrogen-doped carbon material; the hydrolysis catalyst is a solid acid; the mixed solvent includes a polar solvent and water. The method has the advantages of low raw material cost, high conversion rate and product selectivity, mild reaction conditions and the like.
Description
Technical Field
The application relates to a method for preparing glyoxylic acid from methyl glycolate, belonging to the field of organic chemical industry.
Background
Glyoxylic acid is an important organic chemical raw material. Ethyl vanillin made from glyoxylic acid is widely used as an aromatizer for daily chemicals such as cosmetics. Allantoin prepared from glyoxylic acid can be used as plant growth regulator, skin wound healing agent and antiulcer agent, and also has effects in protecting from light, sterilizing, preventing corrosion, relieving pain, resisting oxidation, hydrophilizing and preventing water from diffusing, and can be used as cosmetic additive. Glyoxylic acid is also used for preparing drugs such as p-hydroxyphenylacetic acid, p-hydroxyphenylhydantoin, amoxicillin, cefam penicillin, and atier.
The conventional method for preparing glyoxylic acid has the following problems: (1) oxalic acid electrolysis. The oxalic acid aqueous solution is electrolyzed and reduced to generate a dilute solution of the glyoxylic acid, and then the glyoxylic acid is prepared by evaporation, concentration, freezing and filtration and gradual concentration. The method has high energy consumption. (2) Maleic anhydride ozone oxidation reduction method. Dissolving maleic anhydride in formic acid, introducing ozone for oxidation, and reducing with zinc powder to obtain glyoxylic acid. The method adopts metering reaction, and has the disadvantages of large raw material consumption, high cost and poor operation safety. (3) Condensing dichloroacetic acid and sodium methoxide to obtain dimethoxy sodium acetate, and hydrolyzing with hydrochloric acid to obtain glyoxylic acid. The method has high raw material cost, serious equipment corrosion, large amount of acid wastewater generation and complex post-treatment. (4) The glyoxal is oxidized under the action of a catalyst to prepare the glyoxylic acid. The method has the advantages of difficult control of selectivity, easy generation of byproducts such as oxalic acid and the like due to over oxidation, and low product selectivity.
In recent years, great progress has been made in the production of ethylene glycol from coal via synthesis gas. Methyl glycolate is an intermediate product and a byproduct in the process of preparing ethylene glycol from coal, is used in a high-value manner, and has important significance for increasing economic benefits and promoting the development of the industry of preparing ethylene glycol from coal.
Disclosure of Invention
In order to solve the problems of high energy consumption, large raw material consumption, high cost, poor safety, low product selectivity and the like of the existing glyoxylic acid preparation method, the application provides a method for preparing glyoxylic acid from methyl glycolate, and the method has the advantages of low raw material cost, high conversion rate and product selectivity, mild reaction conditions and the like.
The technical scheme for preparing glyoxylic acid from methyl glycolate comprises the following steps: contacting a material containing methyl glycolate and a mixed solvent with an oxidation catalyst and a hydrolysis catalyst in the presence of an oxygen source to react to obtain glyoxylic acid; wherein, air and/or oxygen is used as an oxygen source; obtaining the oxidation catalyst by loading a metal on a nitrogen-doped carbon material; the hydrolysis catalyst is a solid acid; the mixed solvent includes a polar solvent and water.
According to the invention, the proper reaction solvent can control the selective oxidation of hydroxyl in methyl glycolate into aldehyde group and reduce the occurrence of side reactions such as the continuous oxidation of aldehyde group into carboxyl and the like. Alternatively, the invention adopts trifluoroacetic acid and/or fluorinated alcohol compounds as polar solvents; the fluorinated alcohol compound is at least one selected from 2,2, 2-trifluoroethanol, 2,2,3, 3-tetrafluoropropanol, 1,1,1,3,3, 3-hexafluoro-2-propanol, 2,2,3,4,4, 4-hexafluorobutanol and 2,2,3,3,4,4,5, 5-octafluoro-1-pentanol. The solvents form strong hydrogen bond action with glyoxylic acid due to the strong electron withdrawing effect of fluorine, so that the glyoxylic acid is not favorably oxidized into oxalic acid further, and the high selectivity of the glyoxylic acid is obtained.
According to the invention, water is added into the polar solvent to promote the hydrolysis of the ester group into carboxyl, so that the selectivity of glyoxylic acid is improved.
According to the invention, the catalyst is of great importance. Without catalyst or with low catalyst activity, the conversion of methyl glycolate is very low. When the activity and selectivity of the catalyst are high, the high conversion rate of methyl glycolate and the high selectivity of glyoxylic acid can be obtained.
The catalyst of the invention comprises two parts, namely an oxidation catalyst and a hydrolysis catalyst. The nitrogen-doped carbon material loaded metal is an oxidation catalyst, and the solid acid is a hydrolysis catalyst.
According to the invention, nitrogen has large electronegativity, and can generate positive charge polarization effect on adjacent carbon atoms, improve the positive charge density of the adjacent carbon atoms, facilitate the adsorption of oxygen molecules, promote the oxidation reaction and improve the conversion rate of methyl glycolate.
Optionally, the nitrogen-doped carbon material is selected from nitrogen-doped mesoporous carbon, nitrogen-doped microporous carbon, nitrogen-doped carbon nanotubes, nitrogen-doped carbon fibers, nitrogen-doped graphene, graphite-phase carbon nitride g-C3N4At least one of (1).
Optionally, the metal is selected from at least one of cobalt, manganese, copper, iron.
Alternatively, the solid acid is selected from sulfonic acid resin Amberlyst-15, sulfonic acid resin Amberlyst-35, heteropolyacid, metal oxide supported SO4 2-Solid superacid, metal oxide-supported S2O8 2-At least one of solid super acids.
Optionally, the heteropolyacid is selected from at least one of a phosphotungstic heteropolyacid, a silicotungstic heteropolyacid, and a silicomolybdic heteropolyacid.
Optionally, the metal oxide is selected from ZrO2、Fe2O3At least one of (a).
Optionally, the amount of the oxidation catalyst is 0.1-2.0% by mass of methyl glycolate.
Optionally, the amount of the hydrolysis catalyst is 0.1-2.0% by mass of methyl glycolate.
Optionally, the mass percentage concentration of the methyl glycolate in the reaction system is 10-50%;
the reaction system comprises methyl glycolate, a mixed solvent, an oxidation catalyst and a hydrolysis catalyst.
Preferably, the reaction conditions are: the reaction temperature is 100-180 ℃, the reaction pressure is 0.4-2.0 MPa, and the reaction time is 2-8 h.
Alternatively, the oxidation catalyst is prepared by the following method:
and (2) carrying out roasting reaction on the mixture of the metal salt compound and the nitrogen-doped carbon material in an inactive atmosphere to obtain the nitrogen-doped carbon material supported metal catalyst, namely the oxidation catalyst.
Optionally, the metal salt compound is selected from at least one of cobalt salt, manganese salt, copper salt and iron salt
Optionally, the cobalt salt is selected from at least one of cobalt hydrochloride, cobalt sulfate, cobalt nitrate and cobalt acetate;
the manganese salt is selected from at least one of manganese hydrochloride, manganese sulfate, manganese nitrate and manganese acetate;
the copper salt is at least one selected from copper hydrochloride, copper sulfate, copper nitrate and copper acetate;
the iron salt is at least one selected from the group consisting of iron hydrochloride, iron sulfate, iron nitrate and iron acetate.
Optionally, the roasting conditions are: roasting at the temperature of 600-800 ℃; the roasting time is 3-5 h.
The inert atmosphere may be nitrogen, or an inert gas.
Optionally, the mass ratio of the nitrogen-doped carbon material to the metal salt compound is 3-5: 1.
in this application, trifluoroacetic acid is abbreviated as TFA, 2,2, 2-trifluoroethanol is abbreviated as TFE, 2,2,3, 3-tetrafluoropropanol is abbreviated as TFP, 1,1,1,3,3, 3-hexafluoro-2-propanol is abbreviated as HFIP, 2,2,3,4,4, 4-hexafluorobutanol is abbreviated as HFB, and 2,2,3,3,4,4,5, 5-octafluoro-1-pentanol is abbreviated as OFP.
The beneficial effects that this application can produce include:
according to the method for preparing glyoxylic acid from methyl glycolate, air or oxygen is used as an oxygen source, and the glyoxylic acid is prepared by catalytic conversion of methyl glycolate in a mixed solvent containing a polar solvent and water in the presence of a nitrogen-doped carbon material supported metal catalyst and solid acid.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials in the examples of the present application were all purchased commercially.
Example 1
1.2g of cobalt nitrate hexahydrate was dissolved in 40mL of deionized water, and 4.0g of graphite-phase carbon nitride g-C was added3N4Stirring for 2h, vacuum freeze drying, and calcining at 700 deg.C for 4h under nitrogen protection to obtain 5.4g graphite phase carbon nitride g-C3N4Supported cobalt catalyst (Co/g-C)3N4)。
Adding 0.1g of the catalyst into a 250mL high-pressure reaction kettle filled with 0.1g of sulfonic acid resin Amberlyst-15, 10g of methyl glycolate, 5g of deionized water and 40g of 1,1,1,3,3, 3-hexafluoro-2-propanol, stirring, heating to 150 ℃, introducing oxygen to the pressure of 1.0MPa, reacting for 4h, and carrying out qualitative and quantitative analysis on a reaction product through gas chromatography-mass spectrometry, wherein the conversion rate of methyl glycolate is 99 percent and the selectivity of glyoxylic acid is 99 percent.
Examples 2 to 7
Examples 2 to 7 study the effect of different carbon materials loaded with metals on the reaction, the specific procedure is similar to example 1, except that different metal salt compounds and different carbon materials are used to prepare catalysts, and other reaction conditions are the same as example 1, and the results are shown in table 1.
Example 2 differs from example 1 in that: the metal salt was 1.2g of cobalt acetate hexahydrate; the nitrogen-doped carbon material is 3.6g of nitrogen-doped mesoporous carbon (prepared by a NOMC-3-900-T method according to Soxhun's paper of 2017, university of Li, Zhejiang industries, one-step method for synthesizing nitrogen-doped mesoporous carbon material and Pd-loaded and Ag-catalyzed liquid-phase hydrogenation performance research); roasting at 800 ℃ for 3 h; finally obtaining the nitrogen-doped mesoporous carbon supported cobalt catalyst (Co/N-mesoporous carbon).
Example 3 differs from example 1 in that: the metal salt was 1.2g of manganese chloride tetrahydrate; the nitrogen-doped carbon material is 6g of nitrogen-doped microporous carbon (refer to Wuyang, Guangxi university 2018 Master thesis, preparation of high pyrrole nitrogen-doped microporous carbon and ordered mesoporous Ni/carbon composite material and CO thereof2Adsorption Property "PDA0.3/MA0.7-2 method preparation); roasting at 600 ℃ for 5 h; finally obtaining the nitrogen-doped microporous carbon supported manganese catalyst (Mn/N-microporous carbon).
Example 4 differs from example 1 in that: the metal salt is 1.2g of copper sulfate pentahydrate; the nitrogen-doped carbon material is 4.8g of nitrogen-doped carbon nano tube; finally obtaining the nitrogen-doped carbon nanotube loaded copper catalyst (Cu/N-carbon nanotube).
Example 5 differs from example 1 in that: the metal salt was 1.2g ferric chloride hexahydrate; the nitrogen-doped carbon material is 4.8g of nitrogen-doped carbon fiber (refer to the preparation method of the nitrogen-doped carbon nanofiber and the application thereof in the electrocatalytic hydrogen evolution in 2016 master thesis of Wangshuashuai, Zhejiang university of science and technology); finally obtaining the nitrogen-doped carbon fiber supported iron catalyst (Fe/N-carbon fiber).
Example 6 differs from example 1 in that: the nitrogen-Doped carbon material is 4.8g of nitrogen-Doped Graphene (prepared by referring to methods of DehuiDeng, XiulianPan, Xinhe Bao and the like, heated N-Doped Graphene via Solvothermal Synthesis, chem. Mater,2011,23(5),1188-1193 and NG-1); finally obtaining the nitrogen-doped graphene supported cobalt catalyst (Co/N-graphene).
Example 7 differs from example 1 in that: activated carbon is used to replace graphite phase carbon nitride g-C3N4(ii) a Finally obtaining the active carbon supported cobalt catalyst (Co/active carbon).
In examples 2 to 6, nitrogen-doped mesoporous carbon-supported cobalt, nitrogen-doped microporous carbon-supported manganese, nitrogen-doped carbon nanotube-supported copper, nitrogen-doped carbon fiber-supported iron, and nitrogen-doped graphene-supported cobalt were used as oxidation catalysts, respectively, and the conversion rate of methyl glycolate was more than 85%, and the selectivity of glyoxylate was more than 85%. Example 7 using activated carbon supported cobalt as the oxidation catalyst, the methyl glycolate conversion was only 52% and the glyoxylate selectivity was 85%. Examples 1-7 demonstrate that nitrogen doping of the carbon material in the catalyst is beneficial for increasing the conversion of methyl glycolate.
TABLE 1 catalytic effect of different carbon material supported metal catalysts
| Examples | Catalyst and process for preparing same | Methyl glycolate conversion% | Glyoxylate selectivity,% |
| 1 | Co/g-C3N4 | 99 | 99 |
| 2 | Co/N-mesoporous carbon | 96 | 98 |
| 3 | Mn/N-microporous carbon | 88 | 95 |
| 4 | Cu/N-carbon nanotubes | 86 | 90 |
| 5 | Fe/N-carbon fiber | 85 | 86 |
| 6 | Co/N-graphene | 86 | 91 |
| 7 | Co/activated carbon | 52 | 85 |
Examples 8 to 14
Examples 8 to 14 were conducted to examine the influence of the solid acid on the reaction, and the specific procedure was similar to example 1, except that the sulfonic acid resin Amberlyst-15 in example 1 was replaced with a different solid acid or no solid acid was added, as shown in table 2, and the other reaction conditions were the same as those in example 1, and the results are shown in table 2. Examples8 to 13 sulfonic acid resins Amberlyst-35 and SO are used respectively4 2-/ZrO2、S2O8 2-/Fe2O3The catalyst is composed of phosphotungstic heteropoly acid, silicotungstic heteropoly acid and silicomolybdic heteropoly acid, the conversion rate of methyl glycolate is above 98%, and the selectivity of glyoxylic acid is above 90%. Example 14 without the use of a hydrolysis catalyst, the methyl glycolate conversion was 99%, but the glyoxylate selectivity was only 46%. Examples 8-14 demonstrate that the hydrolysis catalyst plays a key role in increasing the selectivity of glyoxylic acid.
TABLE 2 Effect of different solid acids on the reaction
| Examples | Solid acid | Conversion of methyl glycolate% | Glyoxylate selectivity,% |
| 8 | Amberlyst-35 | 99 | 96 |
| 9 | SO4 2-/ZrO2 | 99 | 91 |
| 10 | S2O8 2-/Fe2O3 | 98 | 94 |
| 11 | H3PW12O40 | 98 | 90 |
| 12 | H4SiW12O40 | 99 | 98 |
| 13 | H4SiMo12O40 | 98 | 95 |
| 14 | Is free of | 99 | 46 |
Examples 15 to 21
Examples 15 to 21 study the influence of different reaction conditions, and the specific procedure is similar to example 1, except that the responses of different polar solvents, oxidation catalysts, hydrolysis catalysts, substrate concentrations, reaction temperatures, reaction pressures, and reaction times to the catalytic effect are studied, and the other reaction conditions are the same as example 1, and the results are shown in table 3. In a mixed solvent of a fluorinated alcohol compound such as trifluoroacetic acid (TFA), 2,2, 2-Trifluoroethanol (TFE), 2,2,3, 3-Tetrafluoropropanol (TFP), 1,1,1,3,3, 3-hexafluoro-2-propanol (HFIP), 2,2,3,4,4, 4-Hexafluorobutanol (HFB), 2,2,3,3,4,4,5, 5-octafluoro-1-pentanol (OFP) and water, Co/g-C3N4And sulfonic acid resin AmThe mass of both catalysts is 0.1-2.0% of that of methyl glycolate, the mass percentage concentration of a methyl glycolate reaction substrate is 10-50%, the reaction temperature is 100-180 ℃, the reaction pressure is 0.4-2.0 MPa, the reaction time is 2-8 h, the conversion rate of methyl glycolate can reach more than 80%, and the selectivity of glyoxylic acid can reach more than 90%. Example 21 the same reaction conditions as example 1 were used to replace trifluoroacetic acid or fluorinated alcohols with 2-propanol (IPA) to achieve 99% conversion of methyl glycolate but only 52% selectivity to glyoxylic acid, indicating that trifluoroacetic acid and fluorinated alcohols are beneficial to achieving high selectivity to glyoxylic acid.
TABLE 3 reaction conditions for Co/g-C3N4And Effect of the catalytic Effect of sulfonic acid resin Amberlyst-15
In the present application, "substrate concentration" means the mass percentage concentration of methyl glycolate in a reaction system composed of methyl glycolate, a mixed solvent, an oxidation catalyst and a hydrolysis catalyst.
In the invention, air or oxygen is used as an oxygen source, under the condition that a nitrogen-doped carbon material supported metal catalyst and solid acid exist in a mixed solvent of a polar solvent and water, methyl glycolate is catalytically converted to prepare glyoxylic acid, the conversion rate of methyl glycolate and the selectivity of glyoxylic acid can reach 99 percent at most, and the method has the advantages of low raw material cost, high conversion rate and product selectivity, mild reaction conditions and the like.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (9)
1. A method for preparing glyoxylic acid from methyl glycolate is characterized in that a material containing methyl glycolate and a mixed solvent is contacted with an oxidation catalyst and a hydrolysis catalyst in the presence of an oxygen source to react to obtain glyoxylic acid;
wherein, air and/or oxygen is used as an oxygen source;
obtaining the oxidation catalyst by loading a metal on a nitrogen-doped carbon material;
the hydrolysis catalyst is a solid acid;
the mixed solvent comprises a polar solvent and water;
the polar solvent is at least one of fluorinated alcohol compounds and trifluoroacetic acid;
the metal is selected from at least one of cobalt, manganese, copper and iron;
the oxidation catalyst is prepared by the following method:
and (2) carrying out roasting reaction on the mixture of the metal salt compound and the nitrogen-doped carbon material in an inactive atmosphere to obtain the nitrogen-doped carbon material supported metal catalyst, namely the oxidation catalyst.
2. The method according to claim 1, wherein the fluorinated alcohol compound is at least one selected from the group consisting of 2,2, 2-trifluoroethanol, 2,2,3, 3-tetrafluoropropanol, 1,1,1,3,3, 3-hexafluoro-2-propanol, 2,2,3,4,4, 4-hexafluorobutanol, and 2,2,3,3,4,4,5, 5-octafluoro-1-pentanol.
3. The method of claim 1, wherein the nitrogen-doped carbon material is selected from nitrogen-doped mesoporous carbon, nitrogen-doped microporous carbon, nitrogen-doped carbon nanotubes, nitrogen-doped carbon fibers, nitrogen-doped graphene, graphite-phase carbon nitride g-C3N4At least one of (1).
4. The method of claim 1, wherein the solid acid is selected from the group consisting of sulfonic acid resin Amberlyst-15, sulfonic acid resin Amberlyst-35, heteropolyacids, and SO supported on metal oxides4 2-Solid bodySuper strong acid, metal oxide loaded S2O8 2-At least one of solid super acids.
5. The method according to claim 1, wherein the amount of the oxidation catalyst is 0.1-2.0% by mass of methyl glycolate;
the dosage of the hydrolysis catalyst is 0.1-2.0% of the mass of the methyl glycolate;
the mass percentage concentration of the methyl glycolate in the reaction system is 10-50%;
wherein the reaction system comprises methyl glycolate, a mixed solvent, an oxidation catalyst and a hydrolysis catalyst;
the reaction temperature is 100-180 DEG CoC, the reaction pressure is 0.4-2.0 MPa, and the reaction time is 2-8 h.
6. The method according to claim 1, wherein the metal salt compound is at least one selected from the group consisting of cobalt salts, manganese salts, copper salts, and iron salts.
7. The method according to claim 6, wherein the cobalt salt is selected from at least one of cobalt hydrochloride, cobalt sulfate, cobalt nitrate, and cobalt acetate;
the manganese salt is selected from at least one of manganese hydrochloride, manganese sulfate, manganese nitrate and manganese acetate;
the copper salt is at least one selected from copper hydrochloride, copper sulfate, copper nitrate and copper acetate;
the iron salt is at least one selected from the group consisting of iron hydrochloride, iron sulfate, iron nitrate and iron acetate.
8. The method of claim 1, wherein the firing conditions are: the roasting temperature is 600-800 ℃; the roasting time is 3-5 h.
9. The method according to claim 1, wherein the mass ratio of the nitrogen-doped carbon material to the metal salt compound is 3-5: 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2004115426A (en) * | 2002-09-26 | 2004-04-15 | Nippon Shokubai Co Ltd | METHOD FOR PRODUCING alpha-OXOCARBOXYLIC ACID ESTER AND alpha-OXOCARBOXYLIC ACID |
| CN107876055A (en) * | 2017-11-24 | 2018-04-06 | 上海应用技术大学 | A kind of methyl glycollate glyoxalic acid catalyst, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004115426A (en) * | 2002-09-26 | 2004-04-15 | Nippon Shokubai Co Ltd | METHOD FOR PRODUCING alpha-OXOCARBOXYLIC ACID ESTER AND alpha-OXOCARBOXYLIC ACID |
| CN107876055A (en) * | 2017-11-24 | 2018-04-06 | 上海应用技术大学 | A kind of methyl glycollate glyoxalic acid catalyst, preparation method and application |
Non-Patent Citations (1)
| Title |
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| 乙醇酸甲酯法制备乙醛酸;周维友 等;《化工进展》;20111231;第30卷(第11期);2536-2539 * |
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