Process method for electrochemically producing peracetic acid under all-solid-state condition

Abstract

The invention belongs to the technical field of electrochemical synthesis, and particularly relates to a process method for electrochemically producing peracetic acid under an all-solid-state condition. An all-solid-state electrolytic cell reaction device comprises an anode system, a cathode system and a proton exchange membrane between the anode system and the cathode system, the anode system comprises an anode module far away from proton exchange and an anode electrode close to the proton exchange membrane, a first heating device is arranged in the anode module, the anode electrode adopts an IrO2 electrode, and a second heating device is arranged in the cathode system. A current collector for improving the electron conduction efficiency is also arranged between the anode electrode and the anode module; the cathode system comprises a cathode module of a far proton exchange membrane and a cathode electrode of a near proton exchange membrane, a second heating device is arranged in the cathode module, and the cathode electrode adopts a gas diffusion electrode. The reaction process is green and environment-friendly, the technological process is simple, the safety performance is remarkably improved, the reaction efficiency is high, industrial application is easy, and good industrial application prospects are achieved.

Description

Technical Field

[0001] This invention belongs to the field of electrochemical synthesis technology, specifically relating to a process for electrochemically producing peracetic acid under all-solid-state conditions. Background Technology

[0002] Peracetic acid (PAA), as a highly efficient and green oxidant, is widely used in environmental remediation, medical device disinfection, and organic synthesis. Currently, its industrial production mainly relies on traditional chemical synthesis methods, namely the reaction of acetic acid (or anhydride) with hydrogen peroxide under the catalysis of a strong acid (such as sulfuric acid). This method has several inherent drawbacks: First, the strong acid catalyst and excess hydrogen peroxide introduced into the reaction system need to be removed through complex separation and purification steps in subsequent processes, resulting in a long process flow and high energy consumption; second, residual strong acid in the system may catalyze the decomposition of peracetic acid, posing certain safety hazards, while high concentrations of hydrogen peroxide also bring storage and transportation risks; furthermore, the reaction efficiency and selectivity of this method still need improvement, and the reaction cycle is relatively long.

[0003] To overcome the aforementioned problems, electrochemical synthesis has attracted attention due to its mild reaction conditions and clean process. Existing electrochemical methods mostly employ liquid electrolyte systems, generating hydrogen peroxide through a cathode oxygen reduction reaction, which then reacts with acetic acid to produce peracetic acid. However, such methods typically face issues such as electrolyte residue contamination, the need for subsequent separation, and reaction rate limitations due to low gas-liquid-solid three-phase mass transfer efficiency. Developing an integrated electrochemical process that enables efficient in-situ synthesis of peracetic acid without the need for external electrolytes and solvents is of great significance for improving the safety, economy, and product purity of the production process, and is also a technical challenge that those skilled in the art are striving to solve.

[0004] Patent CN 118292001 A discloses a process for the in-situ electrocatalytic oxidation synthesis of peracetic acid based on a stacked electrolytic cell device. This patented method uses acetic acid as the reaction substrate and employs a stacked electrolytic cell device under constant current conditions. An oxygen reduction reaction occurs in situ through a coupled cathode gas diffusion electrode to generate hydrogen peroxide, thus producing peracetic acid. However, this method still utilizes a traditional liquid system reaction method containing electrolytes. This method lacks safety and is prone to producing residual contaminants, causing significant inconvenience in subsequent separation of the purified product. Summary of the Invention

[0005] To address the problems existing in the prior art, the purpose of this invention is to design and provide a process for the electrochemical production of peracetic acid under all-solid-state conditions.

[0006] The present invention is specifically implemented using the following technical solutions: The first aspect of this invention provides an all-solid-state electrolytic cell reactor, comprising an anode system, a cathode system, and a proton exchange membrane between the two systems. The anode system includes a far-proton exchange anode module and a near-proton exchange membrane anode electrode. The anode module is equipped with a first heating device. The anode electrode is an IrO2 electrode. A current collector is also provided between the anode electrode and the anode module to improve electron conduction efficiency. The cathode system includes a cathode module at the far proton exchange membrane and a cathode electrode at the near proton exchange membrane. The cathode module is equipped with a second heating device, and the cathode electrode is a gas diffusion electrode.

[0007] Furthermore, the anode module and cathode module are made of one of silver, titanium, or stainless steel, wherein the titanium surface is plated with Au or Pt with a thickness of 1.5-5 μm.

[0008] Furthermore, the material of the current collector is selected from one of the following: carbon paper, titanium felt, titanium mesh, nickel mesh, nickel felt, Pt-plated titanium felt, Pt-plated nickel felt, Pt-plated titanium mesh, and Pt-plated titanium mesh.

[0009] Furthermore, the IrO2 electrode is prepared by the following steps: dispersing IrO2 in a mixed solution of isopropanol and Nafion, ultrasonically mixing until homogeneous, and spraying it onto one side of a proton exchange membrane. The amount of Nafion in the mixed solution of isopropanol and Nafion is 0.5-2 mg / mL, and the IrO2 loading is 0.5-3 mg / mL. 2 .

[0010] Furthermore, the gas diffusion electrode is prepared by the following steps: (K.1) Graphene powder and Pd precursor were co-dispersed in an acidic aqueous solution and subjected to ultrasonic treatment to ensure thorough mixing and the formation of a uniform dispersion system. (K.2) An electrode support material with gas-repellent properties is used as the cathode, and one side is coated with epoxy resin to protect it from deposition; a Pt sheet is used as the anode, and electrodeposition is performed under step current conditions to achieve uniform loading of Pd active components on the surface of the graphene carrier. (K.3) After electrodeposition, the obtained electrode is thoroughly washed and the resin is removed. Then it is dried to finally obtain a graphene-supported Pd catalyst gas diffusion electrode.

[0011] A second aspect of this invention provides a method for preparing a gas diffusion electrode with a graphene-supported Pd catalyst, comprising the following steps: (K.1) Graphene powder and Pd precursor were co-dispersed in an acidic aqueous solution and subjected to ultrasonic treatment to ensure thorough mixing and the formation of a uniform dispersion system. (K.2) An electrode support material with gas-repellent properties is used as the cathode, and one side is coated with epoxy resin to protect it from deposition; a Pt sheet is used as the anode, and electrodeposition is performed under step current conditions to achieve uniform loading of Pd active components on the surface of the graphene carrier. (K.3) After electrodeposition, the obtained electrode is thoroughly washed and the resin is removed. Then it is dried to finally obtain a graphene-supported Pd catalyst gas diffusion electrode.

[0012] Furthermore, in step K.1, the molar ratio of graphene powder to Pd precursor is 50-100:1, and the Pd precursor material is selected as K2PdC. l4 K2PdC l6 One of PdCl2; the acidic aqueous solution is a mixed solution of H2SO4 and HCl.

[0013] The acidic aqueous solution described in this invention is prepared by mixing 1 ml of 1M HCl, 1 ml of 1M H2SO4, and 8 mL of H2O, and the concentration of the acidic aqueous solution is 0.1M.

[0014] Furthermore, the electrode support material with gas-repellent properties mentioned in step K.2 is one of carbon paper, carbon cloth, and carbon felt; the step current is set to 4-8 A for 0.5 s, 0 A for 1.5 s, for a total of 100 cycles.

[0015] A fourth aspect of this invention provides a process for the electrochemical production of peracetic acid under all-solid-state conditions, comprising the following steps: (S.1) The galvanometer wires are connected to the anode and cathode electrodes of the all-solid-state electrolytic cell reactor, respectively. After filtration through cation adsorption resin, pure water is introduced into the anode module as a hydrogen source, and the stability of the reaction interface is maintained by circulating flow. In the cathode module, acetic acid is used as the reaction substrate, and oxygen is introduced together with acetic acid to carry out electrocatalytic reaction under constant current conditions. (S.2) After oxygen diffuses to the surface of the cathode gas diffusion electrode, an oxygen reduction reaction occurs, generating hydrogen peroxide in situ as an oxidation medium, which then efficiently converts acetic acid into peracetic acid.

[0016] Furthermore, the reaction temperature is 20-80℃, and the oxygen flow rate in step S.1 is 10-50 sccm; the cation adsorption resin can be sulfonic acid group, carboxyl group or phenol group.

[0017] The present invention has the following beneficial effects: (1) The reaction process of this invention is green and environmentally friendly: the entire reaction system does not require strong acid catalysts and additional oxidants, thus avoiding safety and environmental problems caused by the use and subsequent treatment of hazardous chemicals.

[0018] (2) The present invention simplifies the process flow: the all-solid system and in-situ synthesis strategy eliminate the need for complex separation and purification steps, significantly shorten the production cycle, and reduce energy consumption and operating costs.

[0019] (3) The safety performance of the present invention is significantly improved: it avoids the storage, transportation and use of high concentration hydrogen peroxide, and the reaction conditions are mild, which fundamentally improves the safety of the production process.

[0020] (4) The present invention has high reaction efficiency: By combining a gas diffusion electrode with a high-performance graphene-supported Pd catalyst, the mass transfer and reaction kinetics at the gas-liquid-solid three-phase interface are greatly improved, and the efficient and high-rate synthesis of peracetic acid is realized.

[0021] (5) The present invention is easy to industrialize: the modular design of the reaction device, the continuous material flow mode and the stable process control make the technology very suitable for scale-up and continuous production, and has good prospects for industrial application. Attached Figure Description

[0022] Figure 1 This is a flowchart of the process route for the present invention.

[0023] Figure 2 This is a diagram of the all-solid-state electrolytic cell reaction apparatus of the present invention.

[0024] Figure 3 The diagram shows the concentration of peracetic acid generated in the embodiments and comparative examples of this invention.

[0025] Figure 4 This is a SEM image of the graphene-supported Pd catalyst in Example 1 of the present invention.

[0026] The following are the labels in the diagram: Anode system 10; Anode module 11; Anode electrode 12; First heating device 13; Current collector 14; Cathode system 20; Cathode module 21; Cathode electrode 22; Second heating device 23; Proton exchange membrane 30. Detailed Implementation

[0027] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that, unless otherwise specified, the following embodiments and features can be combined with each other. Unless otherwise specified, the methods used in the embodiments of the present invention are conventional methods, and the reagents used are commercially available.

[0028] The present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto.

[0029] The carbon paper used in this embodiment of the invention is model SEN23K, with a porosity of 65%; this high porosity means that there is sufficient gas-liquid contact, which is beneficial to the reaction.

[0030] In this embodiment of the invention, the anode module and cathode module of the all-solid-state electrolytic cell reactor are made of stainless steel.

[0031] In all embodiments of the present invention, the IrO2 electrode was prepared as follows: IrO2 was dispersed in a mixed solution of isopropanol and 5 wt.% Nafion solution, and then sprayed onto one side of a proton exchange membrane. The amount of Nafion in the mixed solution of isopropanol and Nafion was 1 mg / mL; the IrO2 loading was 2.5 mg / cm³. 2 .

[0032] In the embodiments of this invention, the current collectors are all made of Pt-plated titanium felt.

[0033] In the embodiments of this invention, the cation adsorption resins are all sulfonic acid-based.

[0034] See the schematic diagram of the all-solid-state electrolytic cell reactor of the present invention. Figure 1 and Figure 2 The reaction system comprises an anode module and a cathode module, separated by a proton exchange membrane. Both the anode and cathode modules are equipped with heating devices to control the reaction temperature. The anode is an IrO2 electrode, further separated from the anode module by a Pt-plated titanium felt; the cathode is a gas diffusion electrode. The anode and cathode are connected to the positive and negative electrodes of a galvanometer via wires, forming a complete electrochemical reaction circuit. During the reaction, pure water is introduced into the anode module; in the cathode module, acetic acid is used as the reaction substrate, and oxygen is simultaneously introduced along with the acetic acid, resulting in an electrocatalytic reaction under constant current conditions.

[0035] Example 1: A process for electrochemical production of peracetic acid under all-solid-state conditions: An all-solid-state electrolytic cell reactor was assembled. The cathode was a gas diffusion electrode with graphene-supported Pd catalyst, the anode was an IrO2 electrode, and the current collector was a Pt-plated titanium felt. The graphene-supported Pd catalyst gas diffusion electrode was prepared by dispersing 70 mmol of graphene powder and 1 mmol of K2PdCl6 (molar ratio 70:1) in 20 mL of 0.5 mL MH2SO4 aqueous solution and ultrasonically mixing to form a uniform dispersion system. Then, carbon paper was used as the cathode, with one side coated with epoxy resin for protection against deposition. A Pt sheet was used as the anode, and electrodeposition was performed under 100 cycles of step conditions: 5 A for 0.5 s and 0 A for 1.5 s. After electrodeposition, the resulting electrode was washed to remove the resin and then dried to obtain the graphene-supported Pd catalyst gas diffusion electrode 1.

[0036] Under conditions of 60℃ (with the internal heating devices of the anode and cathode modules activated), 10 mL of acetic acid was added to the cathode module and circulated at a flow rate of 40 mL / min, while oxygen was introduced at a flow rate of 30 sccm. Similarly, 10 mL of pure water was added to the anode module and circulated at a flow rate of 40 mL / min. Finally, a galvanometer was applied at 50 mA / cm. 2 The reaction was carried out at a current density, and the concentration of the product peracetic acid was determined by chemical titration analysis. Figure 3 As shown.

[0037] Example 2: Example 2: The preparation steps of the gas diffusion electrode are the same as in Example 1, except that the amount of graphene powder is replaced with 50 mmol, and other conditions remain unchanged, so as to obtain the gas diffusion electrode 2 with graphene-supported Pd catalyst.

[0038] Example 3: Example 3 The preparation steps of the gas diffusion electrode are the same as in Example 1, except that the amount of graphene powder is replaced with 60 mmol, and other conditions remain unchanged, so as to obtain the gas diffusion electrode 3 with graphene supported Pd catalyst.

[0039] Example 4: Example 4: The preparation steps of the gas diffusion electrode are the same as in Example 1, except that the amount of graphene powder is replaced with 80 mmol, and other conditions remain unchanged, so as to obtain the graphene-supported Pd catalyst gas diffusion electrode 4.

[0040] Example 5: Example 2: The preparation steps of the gas diffusion electrode are the same as in Example 1, except that the amount of graphene powder is replaced with 90 mmol, and other conditions remain unchanged, so as to obtain the gas diffusion electrode 5 with graphene supported on Pd catalyst.

[0041] Example 6: Example 6 The preparation steps of the gas diffusion electrode are the same as in Example 1, except that the amount of graphene powder is replaced with 100 mmol, and other conditions remain unchanged, so as to obtain the graphene-supported Pd catalyst gas diffusion electrode 6.

[0042] Example 7: Example 7 The preparation steps of the gas diffusion electrode are the same as in Example 1, except that the electrodeposition step condition is 4 A for 0.5 s, that is, the final electrodeposition step condition is 4 A for 0.5 s and 0 A for 1.5 s, for a total of 100 cycles.

[0043] Example 8: Example 8 The preparation steps of the gas diffusion electrode are the same as in Example 1, except that the electrodeposition step condition is 6 A for 0.5 s, that is, the final electrodeposition step condition is 6 A for 0.5 s and 0 A for 1.5 s, for a total of 100 cycles.

[0044] Example 9: Example 9 The preparation steps of the gas diffusion electrode are the same as in Example 1, except that the electrodeposition step condition is 7 A for 0.5 s, that is, the final electrodeposition step condition is 7 A for 0.5 s and 0 A for 1.5 s, for a total of 100 cycles.

[0045] Example 10: Example 10 The preparation steps of the gas diffusion electrode are the same as those in Example 1, except that the electrodeposition step condition is 8 A for 0.5 s, that is, the final electrodeposition step condition is 8 A for 0.5 s and 0 A for 1.5 s, for a total of 100 cycles.

[0046] Example 11: The reaction conditions in Example 11 were the same as in Example 1, except that they were performed at room temperature (25°C, with the heating devices inside the anode and cathode modules turned off).

[0047] Example 12: The reaction conditions in Example 12 were the same as those in Example 1, except that the temperature was 50°C (the heating devices inside the anode and cathode modules were turned on).

[0048] Example 13: The reaction conditions in Example 13 were the same as in Example 1, except that the temperature was 70°C (the heating devices inside the anode and cathode modules were turned on).

[0049] Example 14: The reaction conditions in Example 14 were the same as in Example 1, except that the temperature was 80°C (the heating devices inside the anode and cathode modules were turned on).

[0050] Comparative Example 1: A process for electrochemically producing peracetic acid under all-solid-state conditions includes the following steps: assembling an all-solid-state electrolytic cell reactor; using a carbon nanotube-supported Pd catalyst gas diffusion electrode as the cathode; using an IrO2 electrode as the anode; and using Pt-plated titanium felt as the current collector. The preparation method of the carbon nanotube-supported Pd catalyst gas diffusion electrode involves dispersing 70 mmol of carbon nanotube powder and 1 mmol of K2PdCl6 (molar ratio 70:1) together in 20 mL of 0.5 M H2SO4 aqueous solution, and then ultrasonically mixing them to form a uniform dispersion system. Subsequently, using carbon paper as the cathode, one side is coated with epoxy resin for protection against deposition, and a Pt sheet as the anode, electrodeposition is performed under a step condition of 5 A for 0.5 s and 0 A for 1.5 s for a total of 100 cycles. After electrodeposition, the resulting electrode is washed to remove the resin, and then dried to finally obtain the carbon nanotube-supported Pd catalyst gas diffusion electrode.

[0051] Under conditions of 60℃ (with the internal heating devices of the anode and cathode modules activated), 10 mL of acetic acid was added to the cathode module and circulated at a flow rate of 40 mL / min, while oxygen was introduced at a flow rate of 30 sccm. Similarly, 10 mL of pure water was added to the anode module and circulated at a flow rate of 40 mL / min. Finally, a galvanometer was applied at 50 mA / cm. 2 The reaction was carried out at a current density, and the concentration of the product peracetic acid was determined by chemical titration analysis. Figure 3 As shown.

[0052] Comparative Example 2: A process for electrochemically producing peracetic acid under all-solid-state conditions includes the following steps: assembling an all-solid-state electrolytic cell reactor; using a gas diffusion electrode with a Ketjen black-supported Pd catalyst as the cathode; using an IrO2 electrode as the anode; and using a Pt-plated titanium felt as the current collector. The preparation method of the Ketjen black-supported Pd catalyst gas diffusion electrode involves dispersing 70 mmol of Ketjen black powder and 1 mmol of K2PdCl6 (molar ratio 70:1) together in 20 mL of 0.5 M H2SO4 aqueous solution, and then ultrasonically mixing them to form a uniform dispersion system. Subsequently, using carbon paper as the cathode, one side is coated with epoxy resin for protection against deposition, and a Pt sheet as the anode, electrodeposition is performed under a step condition of 5 A for 0.5 s and 0 A for 1.5 s for a total of 100 cycles. After electrodeposition, the resulting electrode is washed to remove the resin, and then dried to finally obtain the Ketjen black-supported Pd catalyst gas diffusion electrode.

[0053] Under conditions of 60℃ (with the internal heating devices of the anode and cathode modules activated), 10 mL of acetic acid was added to the cathode module and circulated at a flow rate of 40 mL / min, while oxygen was introduced at a flow rate of 30 sccm. Similarly, 10 mL of pure water was added to the anode module and circulated at a flow rate of 40 mL / min. Finally, a galvanometer was applied at 50 mA / cm. 2 The reaction was carried out at a current density, and the concentration of the product peracetic acid was determined by chemical titration analysis. Figure 3 As shown.

[0054] Comparative Example 3: A process for electrochemically producing peracetic acid under all-solid-state conditions includes the following steps: assembling an all-solid-state electrolytic cell reactor; using a Cabot carbon black-supported Pd catalyst gas diffusion electrode as the cathode; using an IrO2 electrode as the anode; and using Pt-plated titanium felt as the current collector. The preparation method of the Cabot carbon black-supported Pd catalyst gas diffusion electrode involves dispersing 70 mmol of Cabot carbon black powder and 1 mmol of K2PdCl6 (molar ratio 70:1) together in 20 mL of 0.5 M H2SO4 aqueous solution, and then ultrasonically mixing them to form a uniform dispersion system. Subsequently, using carbon paper as the cathode, one side is coated with epoxy resin for protection against deposition, and a Pt sheet as the anode, electrodeposition is performed under a step condition of 5 A for 0.5 s and 0 A for 1.5 s for a total of 100 cycles. After electrodeposition, the resulting electrode is washed to remove the resin, and then dried to finally obtain the Cabot carbon black-supported Pd catalyst gas diffusion electrode.

[0055] Under conditions of 60℃ (with the internal heating devices of the anode and cathode modules activated), 10 mL of acetic acid was added to the cathode module and circulated at a flow rate of 40 mL / min, while oxygen was introduced at a flow rate of 30 sccm. Similarly, 10 mL of pure water was added to the anode module and circulated at a flow rate of 40 mL / min. Finally, a galvanometer was applied at 50 mA / cm. 2 The reaction was carried out at a current density, and the concentration of the product peracetic acid was determined by chemical titration analysis. Figure 3 As shown.

[0056] Comparative Example 4: A process for electrochemically producing peracetic acid under all-solid-state conditions includes the following steps: assembling an all-solid-state electrolytic cell reactor; using a graphene-supported Ru catalyst gas diffusion electrode as the cathode; using an IrO2 electrode as the anode; and using Pt-plated titanium felt as the current collector. The graphene-supported Pd catalyst gas diffusion electrode is prepared by dispersing 70 mmol of graphene powder and 1 mmol of RuCl3 (molar ratio 70:1) together in 20 mL of 0.5 M H2SO4 aqueous solution, and then ultrasonically mixing them to form a uniform dispersion system. Subsequently, using carbon paper as the cathode, one side is coated with epoxy resin for protection against deposition, and a Pt sheet is used as the anode. Electrodeposition is performed under 100 cycles of step conditions: 5 A for 0.5 s and 0 A for 1.5 s. After electrodeposition, the resulting electrode is washed to remove the resin, and then dried to finally obtain the graphene-supported Ru catalyst gas diffusion electrode.

[0057] Under conditions of 60℃ (with the internal heating devices of the anode and cathode modules activated), 10 mL of acetic acid was added to the cathode module and circulated at a flow rate of 40 mL / min, while oxygen was introduced at a flow rate of 30 sccm. Similarly, 10 mL of pure water was added to the anode module and circulated at a flow rate of 40 mL / min. Finally, a galvanometer was applied at 50 mA / cm. 2 The reaction was carried out at a current density, and the concentration of the product peracetic acid was determined by chemical titration analysis. Figure 3 As shown.

[0058] according to Figure 3 The experimental results of Examples 1-6 show that by controlling the molar ratio of graphene to Pd precursor (K₂PdCl₆), the strong interaction between the metal and the support can be effectively adjusted. The formation of peracetic acid is optimal when the molar ratio of graphene to K₂PdCl₆ is 70:1, reaching a concentration of 950 mg / L. SEM images of the catalyst material prepared in Example 1 corresponding to this ratio are shown below. Figure 4As shown, a large number of Pd nanoparticles are distributed on the catalyst surface, with uniform particle size and good dispersion. This highly dispersed Pd nanostructure enhances the adsorption capacity for reactants and promotes the timely desorption of peracetic acid, thereby significantly increasing its concentration.

[0059] In Examples 7-10, the influence of electrodeposition current conditions during the fabrication of gas diffusion electrodes was systematically investigated. Experimental results showed that the electrode exhibited optimal performance under the conditions of a step current of 5 A for 0.5 s and 0 A for 1.5 s, repeated 100 times. The applied current intensity during electrodeposition directly affects the size of the Pd nanoparticles and their electronic interactions with the graphene support, thus influencing the overall performance of the catalyst.

[0060] To further investigate the influence of different carbon material supports on the catalytic behavior of Pd, various carbon materials were used as supports in Comparative Examples 1-3 for comparative studies. Performance test results showed that all control materials were inferior to graphene supports in peracetic acid formation efficiency, further highlighting the unique role of graphene in regulating the electronic structure of Pd.

[0061] Furthermore, comparative experiments conducted in Comparative Example 4 using Ru precursor as the control metal also demonstrated that the gas diffusion electrode constructed with graphene-supported Pd catalyst exhibits superior catalytic performance and overall advantages in the electrochemical synthesis of peracetic acid.

[0062] Example 15: like Figure 2 As shown, the present invention provides an all-solid-state electrolytic cell reaction device, which can be divided into an anode system 10, a cathode system 20, and a proton exchange membrane 30 between the two systems.

[0063] The anode system 10 includes an anode module 11 distal to the proton exchange membrane 30 and an anode electrode 12 near the proton exchange membrane 30. The anode module 11 is made of silver, titanium, or stainless steel, with titanium having an Au or Pt plating thickness of 1.5-5 μm. Silver, titanium, and stainless steel have strong conductivity and mechanical strength, allowing for further selection based on the lifespan, performance, and cost of different materials depending on the medium. A first heating device 13 is internally installed in the anode module 11 to control the reaction temperature. The anode electrode 12 is an IrO2 electrode, exhibiting excellent catalytic activity, improving energy conversion efficiency, and possessing good chemical stability and long service life. A current collector 14 is also installed between the anode electrode 12 and the anode module 11 to improve electron conduction efficiency, thereby enhancing the stability of the electrochemical system and extending the overall service life of the device. The material of the current collector 14 is selected from one of the following: carbon paper, titanium felt, titanium mesh, nickel mesh, nickel felt, Pt-plated titanium felt, Pt-plated nickel felt, Pt-plated titanium mesh, and Pt-plated titanium mesh.

[0064] The cathode system 20 includes a cathode module 21 at the distal end of the proton exchange membrane 30 and a cathode electrode 22 at the near end of the proton exchange membrane 30. The cathode module 21 is made of silver, titanium, or stainless steel, wherein the titanium surface is plated with Au or Pt with a thickness of 1.5-5 μm. A second heating device 23 is installed inside the cathode module 21 to control the reaction temperature. The cathode electrode 22 is a gas diffusion electrode.

[0065] Based on the above embodiments, the IrO2 electrode is prepared by the following steps: dispersing IrO2 in a mixed solution of isopropanol and Nafion, ultrasonically mixing until homogeneous, and spraying it onto one side of a proton exchange membrane. The amount of Nafion in the mixed solution of isopropanol and Nafion is 1 mg / mL, and the IrO2 loading is 2.5 mg / mL. 2 .

[0066] Based on the above embodiments, the gas diffusion electrode is prepared by the following steps: (K.1) Graphene powder and Pd precursor K2PdCl6 (molar ratio of 70:1) were co-dispersed in an acidic aqueous solution of H2SO4 and HCl with a concentration of 0.5M. The mixture was ultrasonically treated to ensure thorough mixing and the formation of a uniform dispersion system. (K.2) Carbon paper is used as the cathode, and one side is coated with epoxy resin to protect it from deposition; Pt sheet is used as the anode, and electrodeposition is performed under the condition of step current of 5-6 A for 0.5 S and 0 A for 1.5 S for a total of 100 cycles, so that the Pd active component is uniformly loaded on the surface of the graphene carrier. (K.3) After electrodeposition, the obtained electrode is thoroughly washed and the resin is removed. Then it is dried to finally obtain a graphene-supported Pd catalyst gas diffusion electrode.

[0067] The specific usage process in this embodiment is as follows: The anode and cathode are connected to the positive and negative electrodes of a galvanometer via wires, respectively, forming a complete electrochemical reaction circuit. Pure water is introduced into the anode module as a hydrogen source, and the stability of the reaction interface is maintained through circulation. Acetic acid is used as the reaction substrate in the cathode module, and oxygen is introduced simultaneously with acetic acid to carry out an electrocatalytic reaction under constant current conditions. After oxygen diffuses to the surface of the cathode gas diffusion electrode, an oxygen reduction reaction occurs, generating hydrogen peroxide in situ as an oxidation medium, thereby efficiently converting acetic acid into peracetic acid.

Claims

1. A solid-state electrolytic cell reactor, comprising an anode system (10), a cathode system (20), and a proton exchange membrane (30) between the two systems, characterized in that, The anode system (10) includes an anode module (11) of the distant proton exchange membrane (30) and an anode electrode (12) of the near proton exchange membrane (30). The anode module (11) is provided with a first heating device (13). The anode electrode (12) is an IrO2 electrode. A current collector (14) for improving electron conduction efficiency is also provided between the anode electrode (12) and the anode module (11). The cathode system (20) includes a cathode module (21) of the far proton exchange membrane (30) and a cathode electrode (22) of the near proton exchange membrane (30). The cathode module (21) is equipped with a second heating device (23), and the cathode electrode (22) is a gas diffusion electrode.

2. The all-solid-state electrolytic cell reactor as described in claim 1, characterized in that, The anode module (11) and cathode module (21) are made of silver, titanium, or stainless steel, wherein the titanium surface is plated with Au or Pt with a thickness of 1.5-5 μm.

3. The all-solid-state electrolytic cell reactor as described in claim 1, characterized in that, The material of the current collector (14) is selected from one of the following: carbon paper, titanium felt, titanium mesh, nickel mesh, nickel felt, Pt-plated titanium felt, Pt-plated nickel felt, Pt-plated titanium mesh, and Pt-plated titanium mesh.

4. The all-solid-state electrolytic cell reactor as described in claim 1, characterized in that, The IrO2 electrode is prepared by the following steps: dispersing IrO2 in a mixed solution of isopropanol and Nafion, ultrasonically mixing until homogeneous, and spraying it onto one side of a proton exchange membrane. The amount of Nafion in the mixed solution of isopropanol and Nafion is 0.5-2 mg / mL, and the IrO2 loading is 0.5-3 mg / mL. 2 .

5. The all-solid-state electrolytic cell reactor as described in claim 1, characterized in that, The gas diffusion electrode is prepared by the following steps: (K.1) Graphene powder and Pd precursor were co-dispersed in an acidic aqueous solution and subjected to ultrasonic treatment to ensure thorough mixing and the formation of a uniform dispersion system. (K.2) An electrode support material with gas-repellent properties is used as the cathode, and one side is coated with epoxy resin to protect it from deposition; a Pt sheet is used as the anode, and electrodeposition is performed under step current conditions to achieve uniform loading of Pd active components on the surface of the graphene carrier. (K.3) After electrodeposition, the obtained electrode is thoroughly washed and the resin is removed. Then it is dried to finally obtain a graphene-supported Pd catalyst gas diffusion electrode.

6. A method for preparing a gas diffusion electrode with a graphene-supported Pd catalyst, characterized in that, Includes the following steps: (K.1) Graphene powder and Pd precursor were co-dispersed in an acidic aqueous solution and subjected to ultrasonic treatment to ensure thorough mixing and the formation of a uniform dispersion system. (K.2) An electrode support material with gas-repellent properties is used as the cathode, and one side is coated with epoxy resin to protect it from deposition; a Pt sheet is used as the anode, and electrodeposition is performed under step current conditions to achieve uniform loading of Pd active components on the surface of the graphene carrier. (K.3) After electrodeposition, the obtained electrode is thoroughly washed and the resin is removed. Then it is dried to finally obtain a graphene-supported Pd catalyst gas diffusion electrode.

7. The method for preparing a gas diffusion electrode with graphene-supported Pd catalyst as described in claim 6, characterized in that, In step K.1, the molar ratio of graphene powder to Pd precursor is 50-100:1, and the Pd precursor material is selected as K2PdC. l4 K2PdC l6 One of PdCl2; the acidic aqueous solution is a mixture of H2SO4 and HCl.

8. The method for preparing a graphene-supported Pd catalyst gas diffusion electrode as described in claim 6, characterized in that, The electrode support material with gas-repellent properties mentioned in step K.2 is one of carbon paper, carbon cloth and carbon felt; the step current is set to 4-8 A for 0.5 s and 0 A for 1.5 s, for a total of 100 cycles.

9. A process for producing peracetic acid under all-solid-state conditions using an all-solid-state electrolytic cell reactor as described in any one of claims 1-5, characterized in that, Includes the following steps: (S.1) The galvanometer wires are connected to the anode and cathode electrodes of the all-solid-state electrolytic cell reactor, respectively. After filtration through cation adsorption resin, pure water is introduced into the anode module as a hydrogen source, and the stability of the reaction interface is maintained by circulating flow. In the cathode module, acetic acid is used as the reaction substrate, and oxygen is introduced together with acetic acid to carry out an electrocatalytic reaction under constant current conditions. (S.2) After oxygen diffuses to the surface of the cathode gas diffusion electrode, an oxygen reduction reaction occurs, generating hydrogen peroxide in situ as an oxidation medium, which then efficiently converts acetic acid into peracetic acid.

10. The process for producing peracetic acid under all-solid-state electrochemical conditions as described in claim 9, characterized in that, The reaction temperature is 20-80℃; the oxygen flow rate in step S.1 is 10-50 sccm; the cation adsorption resin can be sulfonic acid group, carboxyl group or phenol group.

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