CN116288423A - Method for preparing glycollic acid by electrocatalytic reduction of oxalic acid under cation regulation - Google Patents

Method for preparing glycollic acid by electrocatalytic reduction of oxalic acid under cation regulation Download PDF

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CN116288423A
CN116288423A CN202211674045.8A CN202211674045A CN116288423A CN 116288423 A CN116288423 A CN 116288423A CN 202211674045 A CN202211674045 A CN 202211674045A CN 116288423 A CN116288423 A CN 116288423A
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oxalic acid
preparing
acid
electrocatalytic reduction
cation
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栗振华
郝蕾蕾
任清汇
周华
邵明飞
段雪
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
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Abstract

The invention provides a method for preparing glycollic acid by electrocatalytic reduction of oxalic acid under cation regulation, which comprises the following steps: preparing an electrolyte containing at least two cations; wherein the electrolyte contains at least one monovalent cation and at least one divalent cation or more; oxalic acid with preset concentration is dissolved in the electrolyte to obtain a reaction solution; assembling an anode catalyst, a cathode catalyst, a diaphragm and a reaction solution into an electrolytic cell; under the conditions of preset temperature, preset voltage and preset pH, the electrolytic cell is electrolyzed, so that oxalic acid is subjected to electrocatalytic reduction at the cathode of the electrolytic cell to generate glycolic acid, and water is subjected to anodic oxidation at the electrolytic cell to generate oxygen. The invention can solve the problems of harsh reaction conditions, high energy consumption, more side reactions, realization of improvement of the performance of preparing the glycolic acid by electrocatalytic oxalic acid through simple regulation and control of cations in electrolyte, low reaction rate and the like in the existing method for preparing the glycolic acid.

Description

Method for preparing glycollic acid by electrocatalytic reduction of oxalic acid under cation regulation
Technical Field
The invention relates to the technical field of glycollic acid production, in particular to a method for preparing glycollic acid by electrocatalytic reduction of oxalic acid under cation regulation.
Background
Glycolic acid is an important chemical intermediate useful in metal cleaning, leather processing, adhesives, and the like. In particular, the polymer (polyglycolic acid) thereof exhibits unique biodegradability and biocompatibility, and is widely used for agricultural films, medical sutures, fracture fixation materials, etc. Glycolic acid is industrially obtainable by oxalic acid reduction or ethylene glycol oxidation. Oxalic acid (OX) is an inexpensive and abundant resource, and can be obtained from carbon dioxide, coal and biomass. Therefore, the production of the glycolic acid with high added value by taking oxalic acid as a raw material has good market application prospect.
Methods for preparing glycolic acid from oxalic acid currently mainly comprise biological methods and chemical methods. The biological method has high safety, but is complex to operate, long in manufacturing period and difficult to realize mass production. Patent (CN 112521265a, 2021) discloses a process for continuous production of glycolic acid from dimethyl oxalate, comprising the steps of: a) After being mixed and preheated, dimethyl oxalate and water undergo an autocatalytic semi-hydrolysis reaction, and the obtained hydrolysate is rectified and purified to obtain monomethyl oxalate; b) And C), carrying out catalytic hydrogenation reaction on the monomethyl oxalate obtained in the step A) and hydrogen under the condition of a catalyst, and rectifying and purifying a reaction product to obtain glycolic acid. The chemical method has high selectivity and is suitable for large-scale production of glycollic acid, but the reaction condition is harsh, hazardous gas (hydrogen) is needed, and the reaction is carried out at high temperature and high pressure, so that the energy consumption is high. Therefore, developing a novel green glycollic acid production process still has great scientific and economic value.
Electrocatalytic reduction is an effective method to replace the cathodic hydrogen evolution reaction with the reduction of organics and to obtain high value added products. Patent (CN 112725825A, 2020) discloses a method for preparing glyoxylic acid by oxalic acid electrolysis, which comprises a desalted water storage tank, a cathode storage tank, an ion membrane electrolytic tank, an anode storage tank, a desalted water pump, a cathode feed pump and an anode circulating pump, wherein an additive dissolving tank is arranged on one side of the desalted water storage tank, and a catholyte buffer tank is arranged between the cathode storage tank and the ion membrane electrolytic tank. The main reaction of the cathode is that oxalic acid is reduced to glyoxylic acid (selectivity is more than 85%), the main product is glyoxylic acid, and the side reaction is more.
Although the electrocatalytic production of glycolic acid from oxalic acid has been reported in the paper (Energy environment. Sci.,2015,8,1456), they have only used sodium sulfate as electrolyte, which has the problem of low current density, and the effect of cations in the electrolyte in solution on performance has not been studied. In the patent, the influence of cations on the performance is emphasized, and the electrolyte containing at least two cations is found to be capable of improving the performance of preparing the glycollic acid by electrocatalytic acid.
Disclosure of Invention
In view of the problems, the invention aims to provide a method for preparing glycolic acid by electrocatalytic reduction of oxalic acid under cation regulation, so as to solve the problems of harsh reaction conditions, high energy consumption, multiple side reactions, low reaction rate and the like in the existing method for preparing glycolic acid.
The invention provides a method for preparing glycollic acid by electrocatalytic reduction of oxalic acid under cation regulation, which comprises the following steps:
preparing an electrolyte containing at least two cations; wherein the electrolyte contains at least one monovalent cation and at least one divalent cation or more;
oxalic acid with preset concentration is dissolved in the electrolyte to obtain a reaction solution;
assembling an anode catalyst, a cathode catalyst, a diaphragm and the reaction solution into an electrolytic cell;
under the conditions of preset temperature, preset voltage and preset pH, the electrolytic cell is electrolyzed, so that oxalic acid is subjected to electrocatalytic reduction at the cathode of the electrolytic cell to generate glycolic acid, and water is subjected to anodic oxidation at the electrolytic cell to generate oxygen.
In addition, preferably, the monovalent cation is any one of sodium ions and potassium ions or two mixed ions mixed according to any proportion; and/or the number of the groups of groups,
the divalent cations are one of magnesium ions, zinc ions, calcium ions and aluminum ions or mixed ions according to any proportion.
In addition, it is preferable that, in the electrolyte, a molar ratio of the monovalent cation to the divalent cation or more is: 1:1 or 1:2 or 1:3 or 2:3.
Further, it is preferable that the anode catalyst is a compound of a transition metal or a noble metal; and/or the cathode catalyst is a compound of a transition metal.
In addition, it is preferable that the compound of the transition metal is one of a sulfide of the transition metal, an oxide of the transition metal, a boride of the transition metal, and a phosphide of the transition metal, or a mixture of several kinds of them in an arbitrary ratio.
In addition, preferably, the transition metal is one of tungsten, chromium, vanadium, manganese, zinc and titanium or several of the transition metals mixed according to any proportion.
In addition, preferably, the noble metal is one of platinum, palladium, rhodium and iridium or several mixed according to any proportion.
Further, it is preferable that the separator is any one of AMI7001, CMI7000, FAA-3-20, nafionXL, nafion, 117.
Furthermore, it is preferable that the preset concentration is 0.5 to 10g/L.
In addition, the preferable scheme is that the preset temperature is 20-60 ℃; and/or, the preset voltage is-10-0V; and/or, the preset pH value is 0-14.
According to the technical scheme, the method for preparing the glycolic acid by the cationic regulation oxalic acid electrocatalytic reduction provided by the invention has the advantages that oxalic acid is dissolved into an electrolytic solution, an anode catalyst, a cathode catalyst, a diaphragm and a reaction solution are assembled into an electrolytic cell, the electrolytic cell is utilized to directly electrolyze the oxalic acid, the main product is the glycolic acid, the side reaction is less, the selectivity is high, the added value is high, the application is wide, and the like; the invention not only obtains the high-purity glycollic acid, but also realizes the purpose of converting oxalic acid into glycollic acid at a high speed under a lower voltage; the invention adopts an electrolyte solution to prepare electrolyte solution containing at least two cations; the electrolyte at least contains one monovalent cation and at least one divalent cation or more, and the electrolyte can mix the monovalent cations with the divalent cations or more to enhance the adsorption of carboxyl on the surface of the catalyst, thereby effectively improving the preparation rate of glycollic acid and the density of generated current.
To the accomplishment of the foregoing and related ends, one or more aspects of the invention comprise the features hereinafter fully described. The following description and the annexed drawings set forth in detail certain illustrative aspects of the invention. These aspects are indicative, however, of but a few of the various ways in which the principles of the invention may be employed. Furthermore, the invention is intended to include all such aspects and their equivalents.
Drawings
Other objects and attainments together with a more complete understanding of the invention will become apparent and appreciated by referring to the following description taken in conjunction with the accompanying drawings. In the drawings:
FIG. 1 is a flow chart of a method for preparing glycolic acid by electrocatalytic reduction of cationic-control oxalic acid according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a method for preparing glycollic acid by electrocatalytic reduction of cation-regulated oxalic acid according to an embodiment of the present invention;
FIG. 3 is a scanning electron microscope image of a cathode catalyst according to an embodiment of the present invention;
FIG. 4 is a graph of electrocatalytic reduction polarization of a cation-regulated oxalic acid according to an embodiment of the present invention;
FIG. 5 is a schematic diagram of the reaction rate of preparing glycolic acid by electrocatalytic reduction of oxalic acid under cation regulation according to an embodiment of the invention.
FIG. 6 is a schematic diagram showing the results of a liquid phase reaction for preparing glycolic acid by electrocatalytic reduction of oxalic acid under cation regulation according to an embodiment of the invention.
The same reference numerals will be used throughout the drawings to refer to similar or corresponding features or functions.
Detailed Description
In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of one or more embodiments. It may be evident, however, that such embodiment(s) may be practiced without these specific details.
Aiming at the problems of harsh reaction conditions, high energy consumption, multiple side reactions and the like in the prior method for preparing the glycollic acid, the method for preparing the glycollic acid by electrocatalytic reduction of the oxalic acid is provided.
Specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
In order to illustrate the method for preparing glycolic acid by electrocatalytic reduction of oxalic acid, which is provided by the invention, fig. 1 shows a flow of a method for preparing glycolic acid by electrocatalytic reduction of oxalic acid under cation regulation according to an embodiment of the invention; FIG. 2 shows a schematic diagram of a method for preparing glycollic acid by electrocatalytic reduction of cation-regulated oxalic acid according to an embodiment of the present invention; FIG. 3 shows a scanning electron microscope of a cathode catalyst according to an embodiment of the present invention; FIG. 4 shows a cation-mediated oxalic acid electrocatalytic reduction polarization curve according to an embodiment of the present invention; FIG. 5 is a schematic diagram of the reaction rate of preparing glycolic acid by electrocatalytic reduction of oxalic acid under cation control according to an embodiment of the present invention; fig. 6 shows a schematic diagram of the liquid phase results of a reaction for preparing glycolic acid by electrocatalytic reduction of cationic-controlled oxalic acid according to an embodiment of the invention. As shown in fig. 1 to 6 together, the method for preparing glycolic acid by electrocatalytic reduction of oxalic acid under cation regulation provided by the invention comprises the following steps:
s1, preparing electrolyte containing at least two cations; wherein the electrolyte contains at least one monovalent cation and at least one divalent cation or more;
s2, dissolving oxalic acid with preset concentration into the electrolyte to obtain a reaction solution;
s3, assembling an anode catalyst, a cathode catalyst, a diaphragm and a reaction solution into an electrolytic cell;
s4, under the conditions of preset temperature, preset voltage and preset pH, the electrolytic cell is electrolyzed, so that oxalic acid is subjected to electrocatalytic reduction at the cathode of the electrolytic cell to generate glycolic acid, and water is subjected to anodic oxidation at the electrolytic cell to generate oxygen.
Oxalic acid is dissolved into an electrolytic solution, an anode catalyst, a cathode catalyst, a diaphragm and the reaction solution are assembled into an electrolytic cell, the oxalic acid is directly electrolyzed by the electrolytic cell, the main product is glycolic acid, the side reaction is less, the selectivity is high, and the advantages of high added value, wide application and the like are achieved; the invention not only obtains the high-purity glycollic acid, but also realizes the purpose of converting oxalic acid into glycollic acid at a high speed under a lower voltage; the invention adopts an electrolyte solution to prepare electrolyte solution containing at least two cations; the electrolyte at least contains one monovalent cation and at least one divalent cation or more, and the electrolyte can mix the monovalent cations with the divalent cations or more to enhance the adsorption of carboxyl on the surface of the catalyst, thereby effectively improving the efficiency and yield of the preparation of the glycollic acid.
As a preferred embodiment of the present invention, monovalent cations are either sodium ions, potassium ions or a mixture of both ions mixed in an arbitrary ratio; and/or the number of the groups of groups,
the divalent cation is one of magnesium ion, zinc ion, calcium ion and aluminum ion or mixed ion according to any proportion.
As a preferred embodiment of the present invention, in the electrolyte, the molar ratio of the monovalent cation to the divalent cation or more is: 1:1 or 1:2 or 1:3 or 2:3.
As a preferred embodiment of the present invention, the anode catalyst is a compound of a transition metal or a noble metal; and/or the cathode catalyst is a compound of a transition metal.
As a preferred embodiment of the present invention, the compound of the transition metal is one of a sulfide of the transition metal, an oxide of the transition metal, a boride of the transition metal, and a phosphide of the transition metal, or several of them are mixed in an arbitrary ratio.
As a preferred embodiment of the present invention, the transition metal is one of tungsten, chromium, vanadium, manganese, zinc, and titanium or several of them mixed according to an arbitrary ratio.
As a preferred embodiment of the present invention, the noble metal is one of platinum, palladium, rhodium and iridium or several of them mixed according to an arbitrary ratio.
As a preferred embodiment of the present invention, the membrane is any one of AMI7001, CMI7000, FAA-3-20, nafion XL, nafion 117.
As a preferred embodiment of the present invention, the preset concentration is 0.5 to 10g/L.
As a preferred embodiment of the present invention, the preset temperature is 20 ℃ to 60 ℃; and/or, the preset voltage is-10-0V; and/or, the preset pH value is 0-14.
In order to better illustrate the method for preparing glycolic acid by electrocatalytic reduction of oxalic acid provided by the invention, the following specific examples are provided.
In order to avoid the accident of the experimental result, the experiments in each example below are all carried out for 10 times, and the data of the experimental result obtained finally are all average values of 10 times of experiments.
Example 1
Electrocatalytic reduction of oxalic acid in pure sodium sulfate solution to glycolic acid
1. 0.5g oxalic acid was dissolved in 30mL of 28.4mg/mL Na 2 SO 4 In solution (ph=2).
2. Titanium dioxide is used as a cathode catalyst (shown in figure 3), foam nickel is used as an anode, and the concentration of Na is 28.4mg/mL respectively 2 SO 4 The solution and the reaction solution prepared in step 1 were subjected to a polarization curve test (voltage range of-1 to 0V, scan rate of 0.02V/s). As shown in FIG. 4, after oxalic acid was added to the sodium sulfate solution, the current density of the polarization curve was 100mA cm at the maximum -2 . The reaction was carried out at 50℃under a constant voltage of-0.8V for 1 hour, as shown in FIG. 5, at a reaction rate of 0.89mmol h -1 cm -2 。
3. Titanium dioxide is used as a cathode catalyst, foam nickel is used as an anode catalyst, and the foam nickel and the reaction liquid prepared in the step 1 form an electrolytic cell, and the electrolytic cell is reacted for 12 hours at 50 ℃ and a constant voltage of-0.8V. Oxalic acid was reduced to glycolic acid at the cathode with a selectivity >95% (as shown in figure 6).
Example 2
Electrocatalytic reduction of oxalic acid in pure potassium sulfate solution to glycolic acid
1. 0.5g oxalic acid was dissolved in 30mL 34.85mg/mLK 2 SO 4 In solution (ph=2).
2. Titanium dioxide is used as a cathode catalyst, foam nickel is used as an anode, and the reaction liquid and 34.85mg/mL K prepared in the step 1 are respectively 2 SO 4 The solution and the medium were subjected to polarization curve test (voltage range of-1 to 0V, scan rate of 0.02V/s). After oxalic acid is added into the potassium sulfate solution, the current density of the polarization curve is 103mA cm at maximum -2 . The reaction is carried out for 1h under the constant voltage of-0.8V at 50 ℃ with the reaction rate of 0.91mmol h -1 cm -2 。
3. Titanium dioxide is used as a cathode catalyst, foam nickel is used as an anode catalyst, and the foam nickel and the reaction liquid prepared in the step 1 form an electrolytic cell, and the electrolytic cell is reacted for 12 hours at 50 ℃ and a constant voltage of-0.8V. Oxalic acid is reduced to glycolic acid at the cathode, selectivity >95%.
Example 3
Electrocatalytic reduction of oxalic acid in 1:3 potassium sulfate solution and sodium sulfate solution to glycolic acid
1. 0.5g oxalic acid was dissolved in 30mL of Na at 7.10mg/mL 2 SO 4 And 26.14mg/mL K 2 SO 4 In solution (ph=2).
2. The polarization curve test (voltage range of-1 to 0V, scan rate of 0.02V/s) was performed in the reaction solution prepared in step 1 using titanium dioxide as a cathode catalyst and foamed nickel as an anode. As shown in FIG. 4, after oxalic acid was added to the sodium sulfate solution, the current density of the polarization curve was 98mA cm at the maximum -2 . The reaction is carried out for 1h under the constant voltage of-0.8V at 50 ℃ with the reaction rate of 0.86mmol h -1 cm -2 。
3. Titanium dioxide is used as a cathode catalyst, foam nickel is used as an anode catalyst, and the foam nickel and the reaction liquid prepared in the step 1 form an electrolytic cell, and the electrolytic cell is reacted for 12 hours at 50 ℃ and a constant voltage of-0.8V. Oxalic acid is reduced to glycolic acid at the cathode, selectivity >95%.
From the results of the glycolic acid reduction in examples 1 to 3, it is apparent that the glycolic acid was produced by directly electrolyzing oxalic acid using an electrolytic cell, and the selectivity of the reduction of oxalic acid to glycolic acid at the cathode was >95%. The selectivity is higher than the prior art.
Example 4
Oxalic acid with a molar ratio of 1:3, preparing glycollic acid by electrocatalytic reduction of sodium sulfate and zinc sulfate electrolyte
1. 0.5g oxalic acid was dissolved in 30mL of 7.10mg/mL Na 2 SO 4 And 24.21mg/ml ZnSO 4 In solution (ph=2).
2. Titanium dioxide is used as a cathode catalyst, nickel sheets are used as anodes, and an electrolytic cell is formed by the titanium dioxide and the reaction liquid prepared in the step 1, so that a polarization curve test (the voltage range is-1-0V, and the scanning rate is 0.02V/s) is performed. As shown in FIG. 4, after oxalic acid was added to the electrolyte, the current density of the polarization curve was 200mA cm at the maximum -2 . The reaction is carried out for 1h under the constant voltage of-0.8V at 50 ℃, as shown in figure 5, the reaction rate can reach 1.41mmol h -1 cm -2 。
3. Titanium dioxide is used as a cathode catalyst, foam nickel is used as an anode catalyst, and the foam nickel and the reaction liquid prepared in the step 1 form an electrolytic cell, and the electrolytic cell is reacted for 12 hours at 50 ℃ and a constant voltage of-0.8V. Oxalic acid is reduced to glycolic acid at the cathode, selectivity >95%.
Example 5
Oxalic acid with a molar ratio of 1:3, preparing glycollic acid by electrocatalytic reduction of potassium sulfate and zinc sulfate electrolyte
1. 0.5g oxalic acid was dissolved in 30mL of 7.10mg/mL K 2 SO 4 And 24.21mg/ml ZnSO 4 In solution (ph=2).
2. Titanium dioxide is used as a cathode catalyst, nickel sheets are used as anodes, and the titanium dioxide is combined with the reaction solution prepared in the step 1The electrolytic cell was subjected to polarization curve test (voltage range of-1 to 0V, scan rate of 0.02V/s). After oxalic acid is added into the electrolyte, the current density of the polarization curve is 195mA cm at maximum -2 . The reaction is carried out for 1h under the constant voltage of-0.8V at 50 ℃, and the reaction rate can reach 1.38mmol h -1 cm -2 。
3. Titanium dioxide is used as a cathode catalyst, foam nickel is used as an anode catalyst, and the foam nickel and the reaction liquid prepared in the step 1 form an electrolytic cell, and the electrolytic cell is reacted for 12 hours at 50 ℃ and a constant voltage of-0.8V. Oxalic acid is reduced to glycolic acid at the cathode, selectivity >95%.
Example 6
Oxalic acid with a molar ratio of 1:3, preparing glycollic acid by electrocatalytic reduction of sodium sulfate and aluminum sulfate electrolyte
1. 0.5g oxalic acid was dissolved in 30mL of 7.10mg/mL Na 2 SO 4 And 51.30mg/ml Al2 (SO 4 ) 3 in solution (ph=2).
2. Titanium dioxide is used as a cathode catalyst, nickel sheets are used as anodes, and an electrolytic cell is formed by the titanium dioxide and the reaction liquid prepared in the step 1, so that a polarization curve test (the voltage range is-1-0V, and the scanning rate is 0.02V/s) is performed. After oxalic acid is added into the electrolyte, the current density of the polarization curve is 191mA cm at maximum -2 . The reaction is carried out for 1h under the constant voltage of-0.8V at 50 ℃, and the reaction rate can reach 1.36mmol h -1 cm -2 。
3. Titanium dioxide is used as a cathode catalyst, foam nickel is used as an anode catalyst, and the foam nickel and the reaction liquid prepared in the step 1 form an electrolytic cell, and the electrolytic cell is reacted for 12 hours at 50 ℃ and a constant voltage of-0.8V. Oxalic acid is reduced to glycolic acid at the cathode, selectivity >95%.
Example 7
Oxalic acid with a molar ratio of 1:3, preparing glycollic acid by electrocatalytic reduction of magnesium sulfate and zinc sulfate electrolyte
1. 0.5g oxalic acid was dissolved in 30mL of 6.02mg/mL MgSO 4 And 24.21mg/ml ZnSO 4 In solution (ph=2).
2. Titanium dioxide is used as a cathode catalyst, nickel sheets are used as anodes, and the anode and the reaction liquid prepared in the step 1 form an electrolytic cell to carry out polarization curveTesting (voltage range-1-0V, scanning rate 0.02V/s). After oxalic acid is added into the electrolyte, the current density of the polarization curve is 150mA cm at maximum -2 . The reaction is carried out for 1h under the constant voltage of-0.8V at 50 ℃, and the reaction rate can reach 1.03mmol h -1 cm -2 。
3. Titanium dioxide is used as a cathode catalyst, foam nickel is used as an anode catalyst, and the foam nickel and the reaction liquid prepared in the step 1 form an electrolytic cell, and the electrolytic cell is reacted for 12 hours at 50 ℃ and a constant voltage of-0.8V. Oxalic acid is reduced to glycolic acid at the cathode, selectivity >95%.
As shown in fig. 4, the polarization curve current density of example 4 is significantly higher than that of example 1 in comparison with examples 1 and 7. As shown in FIG. 5, the reaction rate of example 4 was significantly higher than that of examples 1 and 7.
Thus, as apparent from examples 1 to 7 described above, the electrolyte prepared with monovalent cations and divalent cations or more in the examples of the present invention has a significantly higher polarization curve current density than the electrolyte prepared with monovalent cations alone or divalent cations alone; the reaction rate is also significantly higher than that of electrolytes prepared with monovalent cations alone or with divalent cations alone.
According to the method for preparing the glycolic acid by the cationic regulation and control oxalic acid electrocatalytic reduction, disclosed by the invention, the oxalic acid is dissolved into an electrolytic solution, the anode catalyst, the cathode catalyst, the diaphragm and the reaction solution are assembled into an electrolytic cell, the electrolytic cell is utilized to directly electrolyze the oxalic acid, and the main product is the glycolic acid, so that the method has the advantages of few side reactions, high selectivity, high added value, wide application and the like; the invention not only obtains the high-purity glycollic acid, but also realizes the purpose of converting oxalic acid into glycollic acid at a high speed under a lower voltage; the invention adopts an electrolyte solution to prepare electrolyte solution containing at least two cations; the electrolyte contains at least one monovalent cation and at least one divalent cation or more, and the electrolyte can mix the monovalent cations with the divalent cations or more to enhance the adsorption of carboxyl on the surface of the catalyst, thereby effectively improving the preparation rate of glycollic acid and the density of generated current.
The method for preparing glycolic acid by electrocatalytic reduction of oxalic acid according to the present invention is described above by way of example with reference to the accompanying drawings. However, it will be appreciated by those skilled in the art that various modifications may be made to the method for producing glycolic acid by electrocatalytic reduction of oxalic acid with cation control as set forth in the present invention above without departing from the scope of the invention. Accordingly, the scope of the invention should be determined from the following claims.

Claims (10)

1. A method for preparing glycollic acid by electrocatalytic reduction of oxalic acid under cation regulation is characterized by comprising the following steps:
preparing an electrolyte containing at least two cations; wherein the electrolyte contains at least one monovalent cation and at least one divalent cation or more;
oxalic acid with preset concentration is dissolved in the electrolyte to obtain a reaction solution;
assembling an anode catalyst, a cathode catalyst, a diaphragm and the reaction solution into an electrolytic cell;
under the conditions of preset temperature, preset voltage and preset pH, the electrolytic cell is electrolyzed, so that oxalic acid is subjected to electrocatalytic reduction at the cathode of the electrolytic cell to generate glycolic acid, and water is subjected to anodic oxidation at the electrolytic cell to generate oxygen.
2. The method for preparing glycollic acid by electrocatalytic reduction of oxalic acid under cation regulation according to claim 1,
the monovalent cations are any one of sodium ions and potassium ions or two mixed ions mixed according to any proportion; and/or the number of the groups of groups,
the divalent cations are one of magnesium ions, zinc ions, calcium ions and aluminum ions or mixed ions according to any proportion.
3. The method for preparing glycollic acid by electrocatalytic reduction of oxalic acid under cation regulation according to claim 1,
in the electrolyte, the molar ratio of the monovalent cation to the divalent cation or more is: 1:1 or 1:2 or 1:3 or 2:3.
4. The method for preparing glycollic acid by electrocatalytic reduction of oxalic acid under cation regulation according to claim 1,
the anode catalyst is a compound of transition metal or noble metal; and/or the number of the groups of groups,
the cathode catalyst is a compound of transition metal.
5. The method for preparing glycollic acid by electrocatalytic reduction of cation-regulated oxalic acid according to claim 4,
the compound of the transition metal is one of sulfide of the transition metal, oxide of the transition metal, boride of the transition metal and phosphide of the transition metal or a plurality of compounds mixed according to any proportion.
6. The method for preparing glycollic acid by electrocatalytic reduction of oxalic acid under cation regulation according to claim 5, wherein the transition metal is one of tungsten, chromium, vanadium, manganese, zinc and titanium or a mixture of the two or more of tungsten, chromium, vanadium, manganese, zinc and titanium according to any proportion.
7. The method for preparing glycolic acid by electrocatalytic reduction of oxalic acid under cation control according to claim 5, wherein the noble metal is one of platinum, palladium, rhodium and iridium or a mixture of the noble metals according to any proportion.
8. The method for preparing glycollic acid by electrocatalytic reduction of cationic regulated oxalic acid according to claim 1, wherein the membrane is any one of AMI7001, CMI7000, FAA-3-20, nafion XL, nafion 117.
9. The method for preparing glycollic acid by electrocatalytic reduction of oxalic acid under cation regulation according to claim 1,
the preset concentration is 0.5-10 g/L.
10. The method for preparing glycollic acid by electrocatalytic reduction of oxalic acid under cation regulation according to claim 1,
the preset temperature is 20-60 ℃; and/or the number of the groups of groups,
the preset voltage is-10-0V; and/or the number of the groups of groups,
the preset pH value is 0-14.
CN202211674045.8A 2022-12-26 2022-12-26 Method for preparing glycollic acid by electrocatalytic reduction of oxalic acid under cation regulation Pending CN116288423A (en)

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