Reaction system for synchronously generating ozone and hydrogen peroxide through salt-free electrolysis and application method of reaction system

Abstract

The invention provides a reaction system for synchronously generating ozone and hydrogen peroxide through salt-free electrolysis and an application method of the reaction system, and belongs to the technical field of electro-catalysis green synthesis. The integrated membrane electrode comprises a cathode mass transfer diffusion layer, a cathode catalyst layer, a proton exchange membrane, an anode catalyst layer and an anode mass transfer diffusion layer which are sequentially stacked, and an anode catalyst in the anode catalyst layer comprises nano tin antimony oxide and / or nano platinum black. And a cathode catalyst in the cathode catalyst layer comprises one or more of conductive carbon black, graphite, carbon nanotubes, graphene, acetylene black and activated carbon fibers. The integrated membrane electrode is large in reaction area and high in conversion efficiency, can effectively reduce mass transfer resistance, runs under high current density, and has quick response capability. The reaction system provided by the invention effectively strengthens the gas-liquid two-phase mass transfer of the cathode and the anode.

Description

Technical Field

[0001] The invention relates to the technical field of electrocatalytic green synthesis, and in particular to a reaction system for synchronously generating ozone and hydrogen peroxide by salt-free electrolysis and an application method thereof. Background Art

[0002] A wide variety of organic pollutants in water bodies pose a serious threat to human health and the ecological environment. Advanced oxidation process is a deep purification technology widely used in the field of water treatment. Its core principle is to produce hydroxyl free radicals with strong oxidizing ability to completely degrade organic pollutants non-selectively, thereby achieving the purpose of improving water quality and reducing environmental risks. Hydrogen peroxide (H 2 O 2 ) is used as a precursor of hydroxyl radicals, and ozone (O 3 ) catalytic method to make H 2 O 2 Converted into hydroxyl radicals (reaction 1).

[0003]

[0004] Currently, in hydrogen peroxide (H 2 O 2 ) and ozone (O 3 ) coupled advanced oxidation process, H 2 O 2 and O 3 The two oxidants are usually added from external sources independently. 2 O 2 It has unstable characteristics. If its concentration exceeds 8%, it is a hazardous chemical. The hydrogen peroxide reagent produced by chemical plants has great safety hazards in storage and transportation. Although there is a method of synthesizing H by electrochemical reduction of oxygen, 2 O 2 , but the reaction process usually adds alkali or salt as electrolyte to start the electrochemical process. 3 The main method of producing ozone is corona discharge, which uses a high voltage electric field to form a corona on the surface of a dielectric. The air in the corona area is excited, causing oxygen molecules to break into active oxygen atoms, which further combine with oxygen molecules to form ozone molecules. The corona discharge process may produce byproducts such as nitrogen oxides, which may have an impact on equipment, the environment and the human body. In addition, the ozone gas produced is introduced into the H 2 O 2 After the aqueous solution is used, most of it escapes into the air due to its limited solubility, which is not only wasteful but also causes O 3 Excessive concentration causes ozone pollution. Therefore, the development of H 2 O 2 and O 3The in-situ synchronous green synthesis technology is of great significance. Summary of the invention

[0005] The purpose of the present invention is to provide a reaction system for simultaneously generating ozone and hydrogen peroxide by salt-free electrolysis and an application method thereof, so as to solve the problem of H 2 O 2 and O 3 Unable to synchronize synthesis.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions: The present invention provides an integrated membrane electrode, comprising a cathode mass transfer diffusion layer, a cathode catalyst layer, a proton exchange membrane, an anode catalyst layer and an anode mass transfer diffusion layer which are stacked in sequence; the anode catalyst in the anode catalyst layer comprises nano antimony tin oxide and / or nano platinum black; the cathode catalyst in the cathode catalyst layer comprises one or more of conductive carbon black, graphite, carbon nanotubes, graphene, acetylene black and activated carbon fibers.

[0007] Preferably, the proton exchange membrane is a perfluorosulfonic acid proton exchange membrane; the cathode mass transfer diffusion layer is a hydrophobic carbon paper or a hydrophobic carbon cloth; the anode mass transfer diffusion layer is a titanium fiber felt; the loading amount of the anode catalyst on the proton exchange membrane is 0.5-3.0 mg / cm 2 The cathode catalyst loading on the proton exchange membrane is 4-8 mg / cm 2 .

[0008] The present invention also provides a method for preparing the above-mentioned integrated membrane electrode, comprising the following steps: (1) dispersing an anode catalyst and a first perfluorosulfonic acid membrane solution in a first mixed solvent to obtain an anode catalyst slurry; (2) dispersing the cathode catalyst, the second perfluorosulfonic acid membrane solution, and the polytetrafluoroethylene emulsion in a second mixed solvent to obtain a cathode catalyst slurry; (3) spraying the anode catalyst slurry and the cathode catalyst slurry on both sides of the proton exchange membrane respectively to obtain a proton exchange membrane loaded with the cathode catalyst layer and the anode catalyst layer; (4) The cathode mass transfer diffusion layer is bonded to one side of the proton exchange membrane carrying the cathode catalyst layer, and the anode mass transfer diffusion layer is bonded to one side of the proton exchange membrane carrying the anode catalyst layer, and then hot pressing is performed to obtain an integrated membrane electrode.

[0009] Preferably, in step (1), the mass fraction of the first perfluorosulfonic acid membrane solution is 3-20%; and the dosage ratio of the anode catalyst to the first perfluorosulfonic acid membrane solution is 0.1-0.3 g: 0.5-3 mL.

[0010] Preferably, in step (2), the mass fraction of the second perfluorosulfonic acid membrane solution is 3-20%, and the mass fraction of the polytetrafluoroethylene emulsion is 10-60%; the amount ratio of the cathode catalyst, the second perfluorosulfonic acid membrane solution and the polytetrafluoroethylene emulsion is 0.1-3 g: 0.1-0.8 mL: 0.1-1.0 mL.

[0011] The present invention also provides a reaction system for synchronously generating ozone and hydrogen peroxide by salt-free electrolysis, the reaction system comprising an oxygen supply unit, a pure water supply unit, an electrolysis unit and a control system; The electrolysis unit includes a reaction stack; The reactor stack comprises a cathode terminal plate, a first gasket, a cathode current collecting plate, a second gasket, a cathode current guide plate, a membrane electrode sealing plate, an integrated membrane electrode, an anode current guide plate, a third gasket, an anode current collecting plate, a fourth gasket, and an anode terminal plate which are arranged in sequence.

[0012] Preferably, the oxygen supply unit comprises an air compressor, an air tank, a refrigerated dryer, an oxygen generator, and an oxygen tank connected in sequence; The pure water supply unit comprises a filter, a water supply pump, a reverse osmosis filter, an ion exchange resin filter, and a pure water storage tank which are connected in sequence.

[0013] Preferably, the cathode end plate is provided with a cathode liquid inlet, a cathode gas inlet and a cathode liquid outlet; and the anode end plate is provided with an anode liquid inlet and an anode liquid outlet.

[0014] Preferably, the electrolysis unit further comprises a cathode electromagnetic flowmeter, a cathode heat exchanger, a cathode micro-nano bubble generator, a cathode liquid tank, a cathode metering pump, an anode electromagnetic flowmeter, an anode heat exchanger, an anode micro-nano bubble generator, an anode liquid tank, an anode metering pump, and a DC regulated power supply; The pure water supply unit is connected to the cathode electromagnetic flowmeter and the anode electromagnetic flowmeter through the pure water metering pump, the proportional integral regulator and the one-way check valve to form a pure water supply passage; The cathode electromagnetic flowmeter, cathode heat exchanger, cathode micro-nano bubble generator, reactor stack, cathode liquid tank, and cathode metering pump are sequentially connected to form a cathode circulation loop; The anode electromagnetic flowmeter, anode heat exchanger, reactor stack, anode micro-nano bubble generator, anode liquid tank, and anode metering pump are sequentially connected to form an anode circulation loop; The oxygen supply unit is connected to the cathode air inlet of the reactor stack through an oxygen flow meter and an oxygen pressure transmitter in sequence to form an oxygen supply passage.

[0015] The present invention also provides an application method of the above-mentioned reaction system for simultaneously generating ozone and hydrogen peroxide by salt-free electrolysis, comprising the following steps: S1. Start the pure water supply unit. The pure water in the pure water storage tank enters the pure water supply passage as the electrolyte. Under the action of the proportional integral regulator, it is divided into cathode electrolyte and anode electrolyte. The cathode electrolyte flows through the cathode electromagnetic flowmeter, the cathode heat exchanger, and the cathode micro-nano bubble generator in sequence to enter the reactor stack. The anode electrolyte flows through the anode electromagnetic flowmeter and the anode heat exchanger in sequence to enter the reactor stack. S2. Starting the oxygen supply unit, the oxygen in the oxygen tank enters the reactor through the oxygen supply passage and mixes with the cathode electrolyte to form a gas-water mixture; S3. Start the electrolysis unit, apply a constant current to the DC regulated power supply, and the reactor simultaneously electrolyzes the cathode electrolyte and the anode electrolyte, the hydrogen peroxide solution produced at the cathode enters the cathode liquid tank, and the ozone solution produced at the anode enters the anode liquid tank through the anode micro-nano bubble generator; S4. Start the control system. When the ozone solution in the anode liquid tank reaches the set liquid level, the proportional integral regulator is controlled to stop inputting pure water into the anode side of the reactor stack. At the same time, the anode circulation loop is opened to allow the ozone solution in the anode liquid tank to be circulated and electrolyzed. When the hydrogen peroxide solution in the cathode liquid tank reaches the set liquid level, the pure water supply unit is closed. At the same time, the cathode circulation loop is opened to allow the hydrogen peroxide solution in the cathode liquid tank to be circulated and electrolyzed. When the ozone solution and the hydrogen peroxide solution reach the required concentrations, the electrolysis unit and the oxygen supply unit are closed. In the step S1, the flow ratio of the cathode electrolyte to the anode electrolyte is 1:2-15; the temperature control range of the cathode heat exchanger is 30-80°C; the temperature control range of the anode heat exchanger is 15-50°C; In step S2, the flow ratio of oxygen to cathode electrolyte is 20-120:1.

[0016] Beneficial effects of the present invention: (1) The present invention uses only pure water and air to achieve in-situ synchronous green synthesis of hydrogen peroxide and ozone at the cathode and anode of a single electrochemical reaction stack. This process does not require the addition of additional supporting electrolytes, effectively avoiding the storage, transportation and safety issues caused by the traditional addition of hydrogen peroxide, and solving the problem of byproducts such as nitrogen oxides produced by the traditional corona discharge method.

[0017] (2) The present invention adopts an integrated membrane electrode with a five-layer structure, which has a large reaction area and high conversion efficiency, and can effectively reduce the mass transfer resistance. At the same time, the anode and cathode catalysts are evenly loaded on both sides of the proton exchange membrane in the form of liquid slurry, respectively, to achieve a zero-electrode distance structure of the anode and cathode catalyst layers, so that the membrane electrode can operate at a high current density and have a rapid response capability.

[0018] (3) The present invention utilizes a micro-nano bubble generator to treat the influent water on the cathode side of the reactor stack, which effectively enhances the mass transfer process of the gas-liquid two-phase in the cathode influent water. The guide plate inside the reactor stack has parallel variable diameter flow channels, which can not only enhance the diffusion mass transfer of the reaction medium to the membrane electrode, but also enhance the discharge of the reaction products. In addition, the micro-nano bubble generator is used to treat the products on the anode side of the reactor stack, which effectively enhances the mass transfer efficiency of ozone and thus improves the solubility of ozone in water. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 The structure diagram of the reaction system for the simultaneous generation of ozone and hydrogen peroxide by salt-free electrolysis of the present invention, wherein: 1-air compressor, 2-air tank, 3-refrigerated dryer, 4-oxygen generator, 5-oxygen tank, 6-oxygen flow meter, 7-oxygen pressure transmitter, 8-filter, 9-water supply pump, 10-reverse osmosis filter, 11-ion exchange resin filter, 12-pure water storage tank, 13-pure water level sensor, 14-pure water metering pump, 15-proportional integral regulator, 16-one-way check valve, 17-reverse osmosis filter, 18-ion exchange resin filter, 19-pure water storage tank, 20-pure water level sensor, 21-pure water metering pump, 22-proportional integral regulator, 23-one-way check valve, 24-reverse osmosis filter, 25-ion exchange resin filter, 26-pure water storage tank, 27-pure water level sensor, 28-pure water metering pump, 29-proportional integral regulator, 30-one-way check valve, 31-reverse osmosis filter, 32-ion exchange resin filter, 33-pure water storage tank, 34-pure water level sensor, 35-pure water metering pump, 36-proportional integral regulator, 37-one-way check valve, 38-reverse osmosis filter, 39-ion exchange resin filter, 40-pure water level sensor, 41-pure water metering pump, 42-proportional integral regulator, 43-one-way check valve, 44-one-way check valve, 45-reverse osmosis filter, 46-ion exchange resin filter, 47-pure water level sensor, 48-pure water metering pump, 49-proportional integral regulator, 50-one 7-reactor stack, 18-cathode electromagnetic flowmeter, 19-cathode heat exchanger, 20-cathode micro-nano bubble generator, 21-anode electromagnetic flowmeter, 22-anode heat exchanger, 23-cathode liquid tank, 24-cathode liquid level sensor, 25-hydrogen peroxide concentration sensor, 26-cathode metering pump, 27-anode micro-nano bubble generator, 28-anode liquid tank, 29-anode liquid level sensor, 30-ozone detector, 31-anode metering pump, 32-DC regulated power supply, 33-control system; Figure 2 It is a schematic diagram of the structure of the reactor stack in the present invention, wherein: 1701-cathode terminal plate, 1702-first gasket, 1703-cathode current collecting plate, 1704-second gasket, 1705-cathode guide plate, 1706-membrane electrode sealing plate, 1707-integrated membrane electrode, 1708-anode guide plate, 1709-third gasket, 1710-anode current collecting plate, 1711-fourth gasket, 1712-anode terminal plate; 1713-cathode liquid inlet, 1714-cathode air inlet, 1715-cathode liquid outlet, 1716-anode liquid inlet, 1717-anode liquid outlet; Figure 3 It is a schematic diagram of the structure of the cathode guide plate or the anode guide plate in the reactor stack of the present invention, wherein: 1751 is a guide plate liquid inlet, 1752 is a guide plate flow channel, and 1753 is a guide plate liquid outlet; Figure 4 It is a schematic diagram of the structure of the integrated membrane electrode in the present invention, wherein: 1771-cathode mass transfer diffusion layer, 1772-cathode catalyst layer, 1773-proton exchange membrane, 1774-anode catalyst layer, 1775-anode mass transfer diffusion layer; Figure 5 This is a scanning electron microscope image of the cathode catalyst layer of the integrated membrane electrode in Example 1; Figure 6 This is a scanning electron microscope image of the anode catalyst layer of the integrated membrane electrode in Example 1; Figure 7 This is a test diagram of the hydrophobicity of the cathode mass transfer diffusion layer of the integrated membrane electrode in Example 1; Figure 8 This is a concentration test diagram for the simultaneous generation of ozone and hydrogen peroxide in Application Example 1; Fig. 9 This is a concentration test diagram for the simultaneous generation of ozone and hydrogen peroxide in Application Example 2; Fig.10 This is a concentration test diagram for the simultaneous generation of ozone and hydrogen peroxide in Application Example 3. DETAILED DESCRIPTION

[0020] The present invention provides an integrated membrane electrode, comprising a cathode mass transfer diffusion layer, a cathode catalyst layer, a proton exchange membrane, an anode catalyst layer and an anode mass transfer diffusion layer which are stacked in sequence; the anode catalyst in the anode catalyst layer comprises nano antimony tin oxide and / or nano platinum black; the cathode catalyst in the cathode catalyst layer comprises one or more of conductive carbon black, graphite, carbon nanotubes, graphene, acetylene black and activated carbon fibers.

[0021] In the present invention, the proton exchange membrane is a perfluorosulfonic acid proton exchange membrane; the cathode mass transfer diffusion layer is a hydrophobic carbon paper or a hydrophobic carbon cloth; the anode mass transfer diffusion layer is a titanium fiber felt; the loading amount of the anode catalyst on the proton exchange membrane is 0.5-3.0 mg / cm 2 The cathode catalyst loading on the proton exchange membrane is 4-8 mg / cm 2 .

[0022] In the present invention, the preparation method of the hydrophobic carbon paper or the hydrophobic carbon cloth is: soaking the carbon paper or the carbon cloth in polytetrafluoroethylene emulsion, and then performing heat treatment to obtain the hydrophobic carbon cloth or the hydrophobic carbon paper.

[0023] In the present invention, the thickness of the perfluorosulfonic acid proton exchange membrane is 50~200μm, preferably 60~150μm, and more preferably 80~130μm; the thickness of the cathode mass transfer diffusion layer is 0.1~0.5mm, preferably 0.15~0.4mm, and more preferably 0.19~0.3mm; the thickness of the titanium fiber felt is 0.1~0.4mm, preferably 0.15~0.35mm, and more preferably 0.25mm.

[0024] In the present invention, the surface contact angle of the cathode mass transfer diffusion layer is 130°~160°, preferably 135°~152°, and the porosity is 50~90%, preferably 60~85%, and more preferably 65~78%; the porosity of the anode mass transfer diffusion layer is 50~80%, preferably 60~80%.

[0025] The present invention also provides a method for preparing an integrated membrane electrode, comprising the following steps: (1) dispersing an anode catalyst and a first perfluorosulfonic acid membrane solution in a first mixed solvent to obtain an anode catalyst slurry; (2) dispersing the cathode catalyst, the second perfluorosulfonic acid membrane solution, and the polytetrafluoroethylene emulsion in a second mixed solvent to obtain a cathode catalyst slurry; (3) spraying the anode catalyst slurry and the cathode catalyst slurry on both sides of the proton exchange membrane respectively to obtain a proton exchange membrane loaded with the cathode catalyst layer and the anode catalyst layer; (4) The cathode mass transfer diffusion layer is bonded to one side of the proton exchange membrane carrying the cathode catalyst layer, and the anode mass transfer diffusion layer is bonded to one side of the proton exchange membrane carrying the anode catalyst layer, and then hot pressing is performed to obtain an integrated membrane electrode.

[0026] In the present invention, in the step (1), the mass fraction of the first perfluorosulfonic acid membrane solution is 3-20%, preferably 5-15%, and more preferably 5-10%; the dosage ratio of the anode catalyst to the first perfluorosulfonic acid membrane solution is 0.1-0.3 g:0.5-3 mL, preferably 0.15-0.25 g:1-2.5 mL, and more preferably 0.15 g:1.5-2 mL.

[0027] In the present invention, the first mixed solvent and the second mixed solvent are a mixture of isopropanol and water, and the volume ratio of water to isopropanol is independently 1:1~15, preferably 1:1~4; the amount ratio of the anode catalyst to the first mixed solvent is 0.1~0.3g:10~20mL, preferably 0.15~0.25g:11~15mL, and further preferably 0.15g:12.5~14mL.

[0028] In the present invention, the anode catalyst and the first perfluorosulfonic acid membrane solution are dispersed in the first mixed solvent and preferably subjected to stirring, ultrasound, ball milling and high-speed shearing to obtain the anode catalyst slurry.

[0029] In the present invention, the stirring time is 10 to 60 min, preferably 20 to 50 min, and more preferably 30 to 40 min; the ultrasonic temperature is 5 to 20°C, preferably 8 to 15°C, and the ultrasonic time is 30 to 90 min, preferably 40 to 80 min, and more preferably 45 to 65 min; the ball milling temperature is 3 to 18°C, preferably 5 to 15°C, the ball milling time is 30 to 180 min, preferably 60 to 150 min, and more preferably 90 to 120 min, and the ball milling speed is 100 to 800 rpm, preferably 200 to 600 rpm; the high-speed shearing temperature is 5 to 15°C, preferably 10°C, and the high-speed shearing time is 5 to 40 min, preferably 10 to 30 min, and more preferably 15 to 25 min.

[0030] In the present invention, in the step (2), the mass fraction of the second perfluorosulfonic acid membrane solution is 3-20%, preferably 5-15%, and the mass fraction of the polytetrafluoroethylene emulsion is 10-60%, preferably 20-60%, and more preferably 40-60%; the amount ratio of the cathode catalyst, the second perfluorosulfonic acid membrane solution and the polytetrafluoroethylene emulsion is 0.1-3 g: 0.1-0.8 mL: 0.1-1.0 mL, preferably 0.5-2 g: 0.2-0.6 mL: 0.3-0.8 mL, and more preferably 1.0-1.5 g: 0.4-0.5 mL: 0.4-0.6 mL.

[0031] In the present invention, the usage ratio of the cathode catalyst to the second mixed solvent is 0.1-3 g: 20-40 mL, preferably 0.5-2 g: 25-35 mL, and more preferably 1.0-1.5 g: 30 mL.

[0032] In the present invention, the cathode catalyst, the second perfluorosulfonic acid membrane solution, and the polytetrafluoroethylene emulsion are dispersed in the second mixed solvent and preferably stirred, ultrasonicated, ball-milled, and sand-milled to obtain a cathode catalyst slurry; the stirring time is 30 to 80 minutes, preferably 40 to 70 minutes, and more preferably 50 to 60 minutes; the ultrasonic temperature is 5 to 20°C, preferably 8 to 15°C, and the ultrasonic time is 20 to 100 minutes. min, preferably 40~80min; the temperature of the ball mill is 3~18°C, preferably 5~15°C, the time of the ball mill is 30~240min, preferably 60~180min, more preferably 90~120min, the speed of the ball mill is 200~800rpm, preferably 300~700rpm; the speed of the sand mill is 1000~3200rpm, preferably 1500~3000rpm, more preferably 2000~2500rpm, the time of the sand mill is 10~90min, preferably 20~70min, more preferably 30~50min.

[0033] In the present invention, in the step (3), the slurry pressure during spraying is 0.1~0.6 bar, preferably 0.2~0.5 bar, and more preferably 0.25~0.45 bar; the atomization pressure of spraying is 2.0~5.0 bar, preferably 2.5~4.5 bar, and more preferably 3.5 bar; the spray pressure of spraying is 0.5~3.5 bar, preferably 0.8~2.5 bar, and more preferably 1.2~2.0 bar; the nozzle moving speed is 40~120 mm / min, preferably 50~100 mm / min, and more preferably 60~80 mm / min.

[0034] In the present invention, after spraying, a drying treatment is preferably performed, the drying temperature is 50-70° C., and the drying time is 20-28 hours.

[0035] In the present invention, in the step (4), the temperature of the hot pressing treatment is 80-150°C, preferably 90-130°C, and more preferably 100-120°C; the pressure of the hot pressing treatment is 5-16 MPa, preferably 8-14 MPa, and more preferably 10-12 MPa; the holding time of the hot pressing treatment is 60-600 s, preferably 120-500 s, and more preferably 180-400 s.

[0036] The present invention also provides a reaction system for synchronously generating ozone and hydrogen peroxide by salt-free electrolysis, the reaction system comprising an oxygen supply unit, a pure water supply unit, an electrolysis unit and a control system; The electrolysis unit includes a reaction stack 17; The reactor stack includes a cathode end plate 1701, a first gasket 1702, a cathode current collecting plate 1703, a second gasket 1704, a cathode guide plate 1705, a membrane electrode sealing plate 1706, an integrated membrane electrode 1707, an anode guide plate 1708, a third gasket 1709, an anode current collecting plate 1710, a fourth gasket 1711, and an anode end plate 1712, which are arranged in sequence.

[0037] In the present invention, the oxygen supply unit comprises an air compressor 1, an air tank 2, a refrigerated dryer 3, an oxygen generator 4, and an oxygen tank 5 which are connected in sequence; The pure water supply unit includes a filter 8, a water supply pump 9, a reverse osmosis filter 10, an ion exchange resin filter 11, and a pure water storage tank 12 which are connected in sequence.

[0038] In the present invention, the cathode end plate is provided with a cathode liquid inlet 1713 , a cathode gas inlet 1714 and a cathode liquid outlet 1715 ; and the anode end plate is provided with an anode liquid inlet 1716 and an anode liquid outlet 1717 .

[0039] In the present invention, the cathode guide plate 1705 and the anode guide plate 1708 are provided with a guide plate liquid inlet 1751, a guide plate flow channel 1752, and a guide plate liquid outlet 1753; and the guide plate flow channel is a parallel variable diameter flow channel.

[0040] In the present invention, the electrolysis unit further comprises a cathode electromagnetic flowmeter 18, a cathode heat exchanger 19, a cathode micro-nano bubble generator 20, a cathode liquid tank 23, a cathode metering pump 26, an anode electromagnetic flowmeter 21, an anode heat exchanger 22, an anode micro-nano bubble generator 27, an anode liquid tank 28, an anode metering pump 31, and a DC regulated power supply 32; The pure water supply unit is connected to the cathode electromagnetic flowmeter 18 and the anode electromagnetic flowmeter 21 through the pure water metering pump 14, the proportional integral regulator 15 and the one-way check valve 16 to form a pure water supply passage; The cathode electromagnetic flowmeter 18, cathode heat exchanger 19, cathode micro-nano bubble generator 20, reactor stack 17, cathode liquid tank 23, cathode metering pump 26 are sequentially connected to form a cathode circulation loop; The anode electromagnetic flowmeter 21, the anode heat exchanger 22, the reactor stack 17, the anode micro-nano bubble generator 27, the anode liquid tank 28, and the anode metering pump 31 are sequentially connected to form an anode circulation loop; In the present invention, the oxygen supply unit is connected to the cathode air inlet 1714 of the reactor stack 17 in sequence through the oxygen flow meter 6 and the oxygen pressure transmitter 7 to form an oxygen supply passage.

[0041] In the present invention, the reactor stack 17 is externally connected to a DC regulated power supply 32 .

[0042] In the present invention, the cathode liquid tank 23 is provided with a cathode liquid level sensor 24 and a hydrogen peroxide concentration sensor 25; the anode liquid tank 28 is provided with an anode liquid level sensor 29 and an ozone detector 30; the pure water storage tank 12 is provided with a pure water liquid level sensor 13; the control system 33 is respectively connected to the pure water liquid level sensor 13, the pure water metering pump 14, the proportional integral regulator 15, the cathode electromagnetic flowmeter 18, the cathode liquid level sensor 24, the hydrogen peroxide concentration sensor 25, the cathode metering pump 26, the anode electromagnetic flowmeter 21, the anode liquid level sensor 29, the ozone detector 30, the anode metering pump 31, and the DC regulated power supply 32 to form a control loop.

[0043] The present invention also provides an application method of the above-mentioned reaction system for simultaneously generating ozone and hydrogen peroxide by salt-free electrolysis, comprising the following steps: S1. Start the pure water supply unit, the pure water in the pure water storage tank 12 enters the pure water supply passage as the electrolyte, and is divided into the cathode electrolyte and the anode electrolyte under the action of the proportional integral regulator 15, the cathode electrolyte flows through the cathode electromagnetic flowmeter 18, the cathode heat exchanger 19, and the cathode micro-nano bubble generator 20 to enter the reactor 17, and the anode electrolyte flows through the anode electromagnetic flowmeter 21 and the anode heat exchanger 22 to enter the reactor 17; S2 starts the oxygen supply unit, the oxygen in the oxygen tank 5 enters the reactor stack 17 through the oxygen supply passage and mixes with the cathode electrolyte to form a gas-water mixture; S3. Start the electrolysis unit, the DC regulated power supply 32 applies a constant current, the reactor 17 simultaneously electrolyzes the cathode electrolyte and the anolyte, the hydrogen peroxide solution produced at the cathode enters the cathode tank 23, and the ozone solution produced at the anode enters the anode tank 28 via the anode micro-nano bubble generator 27; S4. Start the control system 33. When the ozone solution in the anode liquid tank 28 reaches the set liquid level, the proportional integral regulator 15 is controlled to stop inputting pure water into the anode side of the reactor stack 17. At the same time, the anode circulation loop is opened to allow the ozone solution in the anode liquid tank 28 to be circulated and electrolyzed. When the hydrogen peroxide solution in the cathode liquid tank 23 reaches the set liquid level, the pure water supply unit is closed. At the same time, the cathode circulation loop is opened to allow the hydrogen peroxide solution in the cathode liquid tank 23 to be circulated and electrolyzed. When the ozone solution and the hydrogen peroxide solution reach the desired concentration, the electrolysis unit and the oxygen supply unit are closed. In the step S1, the flow ratio of the cathode electrolyte to the anode electrolyte is 1:2-15, preferably 1:8-12; the temperature control range of the cathode heat exchanger 19 is 30-80°C, preferably 45-60°C; the temperature control range of the anode heat exchanger 22 is 15-50°C, preferably 30-40°C; In step S2, the flow ratio of oxygen to cathode electrolyte is 20-120:1, preferably 60-100:1.

[0044] In the present invention, the anode electrolyte undergoes a water molecule oxidation reaction in the anode catalyst layer 1774 of the integrated membrane electrode 1707 to produce ozone (reaction formula 2) and a large number of protons. The ozone solution is further enhanced in the mass transfer efficiency of ozone by the anode micro-nano bubble generator 27, and the ozone concentration in the solution is increased, and then enters the anode liquid tank 28, while the protons pass through the proton exchange membrane 1773 and are transmitted to the cathode catalyst layer 1772 to participate in the reaction; on the cathode side, the gas-liquid two-phase mass transfer process in the cathode electrolyte treated by the cathode micro-nano bubble generator 20 is enhanced, and the gas-water mixture formed with the oxygen introduced from the cathode air inlet 1714 undergoes an oxygen molecule reduction reaction in the cathode catalyst layer 1772 of the integrated membrane electrode 1707 to produce hydrogen peroxide (reaction formula 3), and then enters the cathode liquid tank 23 through the cathode liquid outlet 1715.

[0045]

[0046] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0047] Example 1 0.15 g of nano-antimony tin oxide, 10 mL of isopropanol, 1.5 mL of 5% perfluorosulfonic acid membrane solution and 2.5 mL of pure water were mixed, the mixture was stirred for 30 min, ultrasonicated at 8 ° C for 45 min, ball milled at 5 ° C at 500 rpm for 90 min, and high-speed sheared at 10 ° C for 15 min to obtain an anode catalyst slurry.

[0048] 1.0 g of conductive carbon black, 15 mL of isopropanol, 0.4 mL of 5% perfluorosulfonic acid membrane solution, 0.6 mL of 60% polytetrafluoroethylene emulsion and 15 mL of pure water were mixed, the mixture was stirred for 60 min, ultrasonicated at 8 ° C for 40 min, ball milled at 400 rpm at 5 ° C for 90 min, and sand milled at 2500 rpm for 30 min to obtain a cathode catalyst slurry.

[0049] A perfluorosulfonic acid proton exchange membrane with a thickness of 127 μm was selected, and the cathode catalyst slurry and the anode catalyst slurry were sprayed on both sides of the perfluorosulfonic acid proton exchange membrane respectively. The slurry pressure was set to 0.25 bar, the atomization pressure was set to 3.5 bar, the spray pressure was set to 1.2 bar, and the nozzle movement speed was set to 60 mm / min. After spraying, it was dried at 60 ° C for 24 h to obtain a proton exchange membrane loaded with a cathode catalyst layer and an anode catalyst layer, wherein the loading amount of the anode catalyst on the proton exchange membrane was 2 mg / cm 2The loading amount of cathode catalyst on the proton exchange membrane is 6 mg / cm 2 .

[0050] Scanning electron microscopy was used to analyze the cathode catalyst layer and the anode catalyst layer respectively: Figure 5 This is a scanning electron microscope image of the cathode catalyst layer. Figure 6 This is a scanning electron microscope image of the anode catalyst layer. Figure 5 It can be seen that the catalyst in the cathode catalyst layer is uniformly loaded on the proton exchange membrane, the catalyst particle size reaches nanometer level, and the catalyst layer has a rich hierarchical pore structure, which helps to improve the mass transfer effect of oxygen in the cathode oxygen reduction reaction. Figure 6 It can be seen that the catalyst in the anode catalyst layer is relatively densely loaded on the proton exchange membrane, the particle size of the catalyst particles is relatively uniform and reaches the nanometer level, and the uniform catalyst layer can increase the effective active reaction sites for the anode water oxidation reaction.

[0051] Titanium fiber felt with a thickness of 0.25 mm and a porosity of 80% was selected as the anode mass transfer diffusion layer. The titanium fiber felt was polished with 1200 grit sandpaper for 10 min, then immersed in 30wt% NaOH solution for 30 min to remove surface oil, washed with distilled water 3 times, then ultrasonicated in acetone, ethanol and deionized water for 20 min each, and then dried at 60°C for 24h. Carbon paper with a thickness of 0.19 mm and a porosity of 78% was selected as the cathode mass transfer diffusion layer. The carbon paper was immersed in a polytetrafluoroethylene emulsion with a mass fraction of 60% for 60 min, and then heated at 350°C for 4h to obtain hydrophobic carbon paper.

[0052] The hydrophobic carbon paper and titanium fiber felt were respectively combined with the cathode catalyst layer and the anode catalyst layer on the catalyst-coated membrane, and then hot-pressed at a temperature of 120°C with a hot-pressing pressure of 10 MPa and a holding time of 180 s to obtain an integrated membrane electrode.

[0053] The hydrophobicity test and analysis of the cathode mass transfer diffusion layer of the integrated membrane electrode are as follows: Figure 7 As shown, the apparent contact angle of the cathode mass transfer diffusion layer is 152°, indicating that it has strong hydrophobic and aerophilic properties, can stably provide a reaction medium for the cathode oxygen reduction reaction, effectively promote the diffusion and migration of reactants and products, and enhance the mass transfer effect.

[0054] Example 2 0.1 g of nano-platinum black, 10 mL of isopropanol, 0.5 mL of 10% perfluorosulfonic acid membrane solution and 5 mL of pure water were mixed, the mixture was stirred for 60 min, ultrasonicated at 15°C for 30 min, ball milled at 400 rpm at 15°C for 120 min, and high-speed sheared at 5°C for 20 min to obtain an anode catalyst slurry.

[0055] 2.0 g of graphite, 15 mL of isopropanol, 0.2 mL of 10% perfluorosulfonic acid membrane solution, 1.0 mL of 40% polytetrafluoroethylene emulsion and 5 mL of pure water were mixed, the mixture was stirred for 30 min, ultrasonicated at 15°C for 20 min, ball milled at 500 rpm at 15°C for 60 min, and sand milled at 3200 rpm for 50 min to obtain a cathode catalyst slurry.

[0056] A perfluorosulfonic acid proton exchange membrane with a thickness of 80 μm was selected, and the cathode catalyst slurry and the anode catalyst slurry were sprayed on both sides of the perfluorosulfonic acid proton exchange membrane respectively. The slurry pressure was set to 0.30 bar, the atomization pressure was set to 2.5 bar, the spray pressure was set to 2.0 bar, and the nozzle moving speed was set to 100 mm / min. After the spraying was completed, it was dried at 60 ° C for 24 h to obtain a proton exchange membrane loaded with a cathode catalyst layer and an anode catalyst layer, wherein the loading amount of the anode catalyst on the proton exchange membrane was 1 mg / cm 2 The loading amount of cathode catalyst on the proton exchange membrane is 5 mg / cm 2 .

[0057] Titanium fiber felt with a thickness of 0.30 mm and a porosity of 70% was selected as the anode mass transfer diffusion layer. The titanium fiber felt was polished with 1200 mesh sandpaper for 10 min, then immersed in 30wt% NaOH solution for 30 min to remove surface oil, washed with distilled water 3 times, then ultrasonicated in acetone, ethanol and deionized water for 20 min each, and then dried at 60°C for 24h. Carbon cloth with a thickness of 0.25 mm and a porosity of 70% was selected as the cathode mass transfer diffusion layer. The carbon cloth was immersed in a polytetrafluoroethylene emulsion with a mass fraction of 60% for 60 min, and then heated at 350°C for 4h to obtain a hydrophobic carbon cloth.

[0058] The hydrophobic carbon cloth and titanium fiber felt were respectively combined with the cathode catalyst layer and the anode catalyst layer on the catalyst-coated membrane, and then hot-pressed at a temperature of 150°C, a hot-pressing pressure of 5 MPa, and a holding time of 250 s to obtain an integrated membrane electrode.

[0059] Example 3 0.3 g of nano-platinum black, 10 mL of isopropanol, 3 mL of 20% perfluorosulfonic acid membrane solution and 10 mL of pure water were mixed, the mixture was stirred for 10 min, ultrasonicated at 5 ° C for 90 min, ball milled at 600 rpm at 3 ° C for 30 min, and high-speed sheared at 15 ° C for 40 min to obtain an anode catalyst slurry.

[0060] 0.5 g of carbon nanotubes, 15 mL of isopropanol, 0.8 mL of 20% perfluorosulfonic acid membrane solution, 0.4 mL of 10% polytetrafluoroethylene emulsion and 5 mL of pure water were mixed, the mixture was stirred for 80 min, ultrasonicated at 5 ° C for 100 min, ball milled at 600 rpm at 8 ° C for 180 min, and sand milled at 1500 rpm for 20 min to obtain a cathode catalyst slurry.

[0061] A 150 μm thick perfluorosulfonic acid proton exchange membrane was selected, and the cathode catalyst slurry and the anode catalyst slurry were sprayed on both sides of the perfluorosulfonic acid proton exchange membrane, respectively. The slurry pressure was set to 0.45 bar, the atomization pressure was set to 4.5 bar, the spray pressure was set to 0.8 bar, and the nozzle movement speed was set to 50 mm / min. After spraying, it was dried at 60 ° C for 24 h to obtain a proton exchange membrane loaded with a cathode catalyst layer and an anode catalyst layer, wherein the loading amount of the anode catalyst on the proton exchange membrane was 0.8 mg / cm 2 The loading amount of cathode catalyst on the proton exchange membrane is 4 mg / cm 2 .

[0062] A titanium fiber felt with a thickness of 0.15 mm and a porosity of 60% was selected as the anode mass transfer diffusion layer. The titanium fiber felt was polished with 1200 mesh sandpaper for 10 min, then immersed in a 30wt% NaOH solution for 30 min to remove surface oil, washed with distilled water 3 times, and then ultrasonicated in acetone, ethanol and deionized water for 20 min each, and then dried at 60°C for 24h. A carbon cloth with a thickness of 0.15 mm and a porosity of 50% was selected as the cathode mass transfer diffusion layer. The carbon cloth was immersed in a polytetrafluoroethylene emulsion with a mass fraction of 60% for 60 min, and then heated at 350°C for 4h to obtain a hydrophobic carbon cloth.

[0063] The hydrophobic carbon cloth and titanium fiber felt were respectively combined with the cathode catalyst layer and the anode catalyst layer on the catalyst-coated membrane, and then hot-pressed at a temperature of 80°C, a hot-pressing pressure of 16 MPa, and a holding time of 500 s to obtain an integrated membrane electrode.

[0064] Example 4 refer to Figure 1~Figure 4, a reaction system for simultaneously producing ozone and hydrogen peroxide by salt-free electrolysis, comprising an oxygen supply unit, a pure water supply unit, an electrolysis unit and a control system; The oxygen supply unit includes an air compressor 1, an air tank 2, a refrigerated dryer 3, an oxygen generator 4, and an oxygen tank 5 connected in sequence; the pure water supply unit includes a filter 8, a water supply pump 9, a reverse osmosis filter 10, an ion exchange resin filter 11, and a pure water storage tank 12 connected in sequence, wherein a pure water level sensor 13 is provided on the pure water storage tank 12; The electrolysis unit includes a reactor 17, a cathode electromagnetic flowmeter 18, a cathode heat exchanger 19, a cathode micro-nano bubble generator 20, a cathode liquid tank 23, a cathode metering pump 26, an anode electromagnetic flowmeter 21, an anode heat exchanger 22, an anode micro-nano bubble generator 27, an anode liquid tank 28, an anode metering pump 31, and a DC regulated power supply 32, wherein a cathode liquid level sensor 24 and a hydrogen peroxide concentration sensor 25 are arranged on the cathode liquid tank 23, and an anode liquid level sensor 29 and an ozone detector 30 are arranged on the anode liquid tank 28. The reactor 17 includes a cathode end plate 1701, a first gasket 1702, a cathode current collecting plate 1703, a second gasket 1704, a cathode guide plate 1705, a membrane electrode sealing plate 1706, a membrane electrode 1707, an anode guide plate 1708, The third gasket 1709, the anode current collecting plate 1710, the fourth gasket 1711, the anode end plate 1712, the cathode end plate 1701 is provided with a cathode liquid inlet 1713, a cathode gas inlet 1714, and a cathode liquid outlet 1715, the anode end plate 1712 is provided with an anode liquid inlet 1716 and an anode liquid outlet 1717, the cathode current collecting plate 1703 and the anode guide plate 1708 are respectively provided with a guide plate liquid inlet 1751, a guide plate flow channel 1752 (the guide plate flow channel is a parallel variable diameter flow channel), and a guide plate liquid outlet 1753, the integrated membrane electrode 1707 includes a cathode mass transfer diffusion layer 1771, a cathode catalyst layer 1772, a proton exchange membrane 1773, an anode catalyst layer 1774, and an anode mass transfer diffusion layer 1775, and the reactor stack 17 is externally connected to a DC regulated power supply 32; The pure water supply unit is connected to the cathode electromagnetic flowmeter 18 and the anode electromagnetic flowmeter 21 through the pure water metering pump 14, the proportional integral regulator 15, and the one-way check valve 16 to form a pure water supply passage; The oxygen supply unit is connected to the cathode air inlet 1714 of the reactor stack 17 in sequence through the oxygen flow meter 6 and the oxygen pressure transmitter 7 to form an oxygen supply passage; The cathode electromagnetic flowmeter 18, the cathode heat exchanger 19, the cathode micro-nano bubble generator 20, the reaction stack 17, the cathode liquid tank 23, and the cathode metering pump 26 are sequentially connected to form a cathode circulation loop; The anode electromagnetic flowmeter 21, the anode heat exchanger 22, the reactor stack 17, the anode micro-nano bubble generator 27, the anode liquid tank 28, and the anode metering pump 31 are sequentially connected to form an anode circulation loop; The control system 33 is respectively connected to the pure water level sensor 13, the pure water metering pump 14, the proportional integral regulator 15, the cathode electromagnetic flowmeter 18, the cathode liquid level sensor 24, the hydrogen peroxide concentration sensor 25, the cathode metering pump 26, the anode electromagnetic flowmeter 21, the anode liquid level sensor 29, the ozone detector 30, the anode metering pump 31, and the DC regulated power supply 32 to form a control loop.

[0065] Application Example 1 The ozone solution and the hydrogen peroxide solution are prepared using the reaction system for synchronously generating ozone and hydrogen peroxide by salt-free electrolysis of Example 4: the pure water supply unit is started, and under the action of the proportional integral regulator 15, the pure water is divided into the cathode electrolyte and the anolyte according to the flow ratio of 1:8, the cathode electrolyte flows through the cathode electromagnetic flowmeter 18, the cathode electrolyte flow rate is adjusted to 10 mL / min, flows through the cathode heat exchanger 19, the cathode electrolyte temperature is adjusted to 45°C, flows through the cathode micro-nano bubble generator 20 to further improve the gas-liquid mass transfer effect, and then enters the cathode liquid inlet 1713 of the reactor stack 17, the anolyte flows through the anode electromagnetic flowmeter 21, the anode electrolyte flow rate is adjusted to 80 mL / min, flows through the anode heat exchanger 22, and the anode electrolyte temperature is adjusted to 25°C, and then enters the guide plate flow channel 1752 (the guide plate flow channel is a parallel variable diameter flow channel) of the anode guide plate 1708 through the anode liquid inlet 1716 of the reactor stack 17. The oxygen supply unit is started, and the oxygen with a purity higher than 93% in the oxygen tank 5 enters the oxygen supply passage, enters the cathode air inlet 1714 at a flow rate of 600 mL / min, and is fully mixed with the cathode electrolyte flowing into the cathode liquid inlet 1713 to form a gas-water mixture that enters the guide plate flow channel 1752 (the guide plate flow channel is a parallel variable diameter flow channel) of the cathode guide plate 1705. The electrolysis unit is started, and the DC regulated power supply 32 applies current to the cathode current collecting plate 1703 and the anode current collecting plate 1710, and the current density is constant (40 mA / cm 2 ), the reactor 17 simultaneously performs overcurrent electrolysis on the cathode electrolyte and the anode electrolyte, the hydrogen peroxide solution produced by the cathode enters the cathode liquid tank 23 through the cathode liquid outlet 1715, and the ozone solution produced by the anode enters the anode liquid tank 28 through the anode micro-nano bubble generator 27. After 30 minutes, the concentration of the hydrogen peroxide solution in the cathode liquid tank 23 is 157.5 mg / L, and the concentration of the ozone solution in the anode liquid tank 28 is 8.2 mg / L. The test results are as follows: Figure 8 shown.

[0066] Application Example 2 The ozone solution and the hydrogen peroxide solution are prepared using the reaction system for synchronously generating ozone and hydrogen peroxide by salt-free electrolysis of Example 4: the pure water supply unit is started, and under the action of the proportional integral regulator 15, the pure water is divided into the cathode electrolyte and the anolyte according to the flow ratio of 1:10, the cathode electrolyte flows through the cathode electromagnetic flowmeter 18, the cathode electrolyte flow rate is adjusted to 8mL / min, flows through the cathode heat exchanger 19, the cathode electrolyte temperature is adjusted to 50°C, flows through the cathode micro-nano bubble generator 20 to further improve the gas-liquid mass transfer effect, and then enters the cathode liquid inlet 1713 of the reactor stack 17, the anolyte flows through the anode electromagnetic flowmeter 21, the anode electrolyte flow rate is adjusted to 80mL / min, flows through the anode heat exchanger 22, and the anode electrolyte temperature is adjusted to 30°C, and then enters the guide plate flow channel 1752 (the guide plate flow channel is a parallel variable diameter flow channel) of the anode guide plate 1708 through the anode liquid inlet 1716 of the reactor stack 17. The oxygen supply unit is started, and the oxygen with a purity higher than 93% in the oxygen tank 5 enters the oxygen supply passage, enters the cathode air inlet 1714 at a flow rate of 800 mL / min, and is fully mixed with the cathode electrolyte flowing into the cathode liquid inlet 1713 to form a gas-water mixture that enters the guide plate flow channel 1752 (the guide plate flow channel is a parallel variable diameter flow channel) of the cathode guide plate 1705. The electrolysis unit is started, and the DC regulated power supply 32 applies current to the cathode current collecting plate 1703 and the anode current collecting plate 1710, and the current density is constant (60 mA / cm 2 ), the reactor 17 simultaneously performs overcurrent electrolysis on the cathode electrolyte and the anode electrolyte, the hydrogen peroxide solution produced by the cathode enters the cathode liquid tank 23 through the cathode liquid outlet 1715, and the ozone solution produced by the anode enters the anode liquid tank 28 through the anode micro-nano bubble generator 27. After 30 minutes, the concentration of the hydrogen peroxide solution in the cathode liquid tank 23 is 211.4 mg / L, and the concentration of the ozone solution in the anode liquid tank 28 is 14.5 mg / L. The test results are as follows: Fig. 9 shown.

[0067] Application Example 3 The ozone solution and the hydrogen peroxide solution are prepared using the reaction system for synchronously generating ozone and hydrogen peroxide by salt-free electrolysis of Example 4: the pure water supply unit is started, and under the action of the proportional integral regulator 15, the pure water is divided into the cathode electrolyte and the anolyte according to the flow ratio of 1:12, the cathode electrolyte flows through the cathode electromagnetic flowmeter 18, the cathode electrolyte flow rate is adjusted to 15 mL / min, flows through the cathode heat exchanger 19, the cathode electrolyte temperature is adjusted to 60°C, flows through the cathode micro-nano bubble generator 20 to further improve the gas-liquid mass transfer effect, and then enters the cathode liquid inlet 1713 of the reactor stack 17, the anolyte flows through the anode electromagnetic flowmeter 21, the anode electrolyte flow rate is adjusted to 180 mL / min, flows through the anode heat exchanger 22, the anode electrolyte temperature is adjusted to 30°C, and then enters the guide plate flow channel 1752 (the guide plate flow channel is a parallel variable diameter flow channel) of the anode guide plate 1708 through the anode liquid inlet 1716 of the reactor stack 17. The oxygen supply unit is started, and the oxygen with a purity higher than 93% in the oxygen tank 5 enters the oxygen supply passage, enters the cathode air inlet 1714 at a flow rate of 1500 mL / min, and is fully mixed with the cathode electrolyte flowing into the cathode liquid inlet 1713 to form a gas-water mixture that enters the guide plate flow channel 1752 (the guide plate flow channel is a parallel variable diameter flow channel) of the cathode guide plate 1705. The electrolysis unit is started, and the DC regulated power supply 32 applies current to the cathode current collecting plate 1703 and the anode current collecting plate 1710, and the current density is constant (80 mA / cm 2 ), the reactor 17 simultaneously performs overcurrent electrolysis on the cathode electrolyte and the anode electrolyte, the hydrogen peroxide solution produced by the cathode enters the cathode liquid tank 23 through the cathode liquid outlet 1715, and the ozone solution produced by the anode enters the anode liquid tank 28 through the anode micro-nano bubble generator 27. After 30 minutes, the concentration of the hydrogen peroxide solution in the cathode liquid tank 23 is 732.8 mg / L, and the concentration of the ozone solution in the anode liquid tank 28 is 21.6 mg / L. The test results are as follows: Fig.10 shown.

[0068] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. An integrated membrane electrode, characterized in that: It comprises a cathode mass transfer diffusion layer, a cathode catalyst layer, a proton exchange membrane, an anode catalyst layer and an anode mass transfer diffusion layer which are stacked in sequence; the anode catalyst in the anode catalyst layer comprises nano antimony tin oxide and / or nano platinum black; the cathode catalyst in the cathode catalyst layer comprises one or more of conductive carbon black, graphite, carbon nanotubes, graphene, acetylene black and activated carbon fibers.

2. The integrated membrane electrode according to claim 1, characterized in that: The proton exchange membrane is a perfluorosulfonic acid proton exchange membrane; the cathode mass transfer diffusion layer is a hydrophobic carbon paper or a hydrophobic carbon cloth; the anode mass transfer diffusion layer is a titanium fiber felt; the loading amount of the anode catalyst on the proton exchange membrane is 0.5-3.0 mg / cm 2 The cathode catalyst loading on the proton exchange membrane is 4-8 mg / cm 2 .

3. The method for preparing the integrated membrane electrode according to claim 1 or 2, characterized in that: The steps include: (1) dispersing an anode catalyst and a first perfluorosulfonic acid membrane solution in a first mixed solvent to obtain an anode catalyst slurry; (2) dispersing the cathode catalyst, the second perfluorosulfonic acid membrane solution, and the polytetrafluoroethylene emulsion in a second mixed solvent to obtain a cathode catalyst slurry; (3) spraying the anode catalyst slurry and the cathode catalyst slurry on both sides of the proton exchange membrane respectively to obtain a proton exchange membrane loaded with the cathode catalyst layer and the anode catalyst layer; (4) The cathode mass transfer diffusion layer is bonded to one side of the proton exchange membrane carrying the cathode catalyst layer, and the anode mass transfer diffusion layer is bonded to one side of the proton exchange membrane carrying the anode catalyst layer, and then hot pressing is performed to obtain an integrated membrane electrode.

4. The method for preparing an integrated membrane electrode according to claim 3, characterized in that: In the step (1), the mass fraction of the first perfluorosulfonic acid membrane solution is 3-20%; the dosage ratio of the anode catalyst to the first perfluorosulfonic acid membrane solution is 0.1-0.3 g: 0.5-3 mL.

5. The method for preparing an integrated membrane electrode according to claim 3 or 4, characterized in that: In the step (2), the mass fraction of the second perfluorosulfonic acid membrane solution is 3-20%, and the mass fraction of the polytetrafluoroethylene emulsion is 10-60%; the amount ratio of the cathode catalyst, the second perfluorosulfonic acid membrane solution and the polytetrafluoroethylene emulsion is 0.1-3 g: 0.1-0.8 mL: 0.1-1.0 mL.

6. A reaction system for simultaneously producing ozone and hydrogen peroxide by salt-free electrolysis, characterized in that: The reaction system includes an oxygen supply unit, a pure water supply unit, an electrolysis unit and a control system; The electrolysis unit includes a reaction stack; The reactor stack includes a cathode terminal plate, a first gasket, a cathode current collecting plate, a second gasket, a cathode guide plate, a membrane electrode sealing plate, the integrated membrane electrode according to claim 1 or 2, an anode guide plate, a third gasket, an anode current collecting plate, a fourth gasket, and an anode terminal plate, which are arranged in sequence.

7. The reaction system for simultaneously producing ozone and hydrogen peroxide by salt-free electrolysis according to claim 6, characterized in that: The oxygen supply unit comprises an air compressor, an air tank, a refrigerated dryer, an oxygen generator, and an oxygen tank connected in sequence; The pure water supply unit comprises a filter, a water supply pump, a reverse osmosis filter, an ion exchange resin filter, and a pure water storage tank which are connected in sequence.

8. The reaction system for simultaneously producing ozone and hydrogen peroxide by salt-free electrolysis according to claim 6 or 7, characterized in that: The cathode end plate is provided with a cathode liquid inlet, a cathode gas inlet and a cathode liquid outlet; the anode end plate is provided with an anode liquid inlet and an anode liquid outlet.

9. The reaction system for simultaneously producing ozone and hydrogen peroxide by salt-free electrolysis according to claim 8, characterized in that: The electrolysis unit also includes a cathode electromagnetic flowmeter, a cathode heat exchanger, a cathode micro-nano bubble generator, a cathode liquid tank, a cathode metering pump, an anode electromagnetic flowmeter, an anode heat exchanger, an anode micro-nano bubble generator, an anode liquid tank, an anode metering pump, and a DC regulated power supply; The pure water supply unit is connected to the cathode electromagnetic flowmeter and the anode electromagnetic flowmeter through the pure water metering pump, the proportional integral regulator and the one-way check valve to form a pure water supply passage; The cathode electromagnetic flowmeter, cathode heat exchanger, cathode micro-nano bubble generator, reactor stack, cathode liquid tank, and cathode metering pump are sequentially connected to form a cathode circulation loop; The anode electromagnetic flowmeter, anode heat exchanger, reactor stack, anode micro-nano bubble generator, anode liquid tank, and anode metering pump are sequentially connected to form an anode circulation loop; The oxygen supply unit is connected to the cathode air inlet of the reactor stack through an oxygen flow meter and an oxygen pressure transmitter in sequence to form an oxygen supply passage.

10. The application method of the reaction system for simultaneously producing ozone and hydrogen peroxide by salt-free electrolysis according to any one of claims 6 to 9, characterized in that: The steps include: S1. Start the pure water supply unit. The pure water in the pure water storage tank enters the pure water supply passage as the electrolyte. Under the action of the proportional integral regulator, it is divided into cathode electrolyte and anode electrolyte. The cathode electrolyte flows through the cathode electromagnetic flowmeter, the cathode heat exchanger, and the cathode micro-nano bubble generator in sequence to enter the reactor stack. The anode electrolyte flows through the anode electromagnetic flowmeter and the anode heat exchanger in sequence to enter the reactor stack. S2. Starting the oxygen supply unit, the oxygen in the oxygen tank enters the reactor through the oxygen supply passage and mixes with the cathode electrolyte to form a gas-water mixture; S3. Start the electrolysis unit, apply a constant current to the DC regulated power supply, and the reactor simultaneously electrolyzes the cathode electrolyte and the anode electrolyte, the hydrogen peroxide solution produced at the cathode enters the cathode liquid tank, and the ozone solution produced at the anode enters the anode liquid tank through the anode micro-nano bubble generator; S4. Start the control system. When the ozone solution in the anode liquid tank reaches the set liquid level, the proportional integral regulator is controlled to stop inputting pure water into the anode side of the reactor stack. At the same time, the anode circulation loop is opened to allow the ozone solution in the anode liquid tank to be circulated and electrolyzed. When the hydrogen peroxide solution in the cathode liquid tank reaches the set liquid level, the pure water supply unit is closed. At the same time, the cathode circulation loop is opened to allow the hydrogen peroxide solution in the cathode liquid tank to be circulated and electrolyzed. When the ozone solution and the hydrogen peroxide solution reach the required concentrations, the electrolysis unit and the oxygen supply unit are closed. In the step S1, the flow ratio of the cathode electrolyte to the anode electrolyte is 1:2-15; the temperature control range of the cathode heat exchanger is 30-80°C; the temperature control range of the anode heat exchanger is 15-50°C; In step S2, the flow ratio of oxygen to cathode electrolyte is 20-120:1.

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