Electrocatalytic flow reactor and its parallel and series connection structure and processing method

Abstract

The electro-catalytic flow reaction device comprises a membrane electrode and a gas diffusion electrode, a liquid outlet electrode plate is arranged between the membrane electrode and the gas diffusion electrode, an anion exchange membrane is arranged between the liquid outlet electrode plate and the gas diffusion electrode, an anode electrode plate is arranged on the side of the membrane electrode away from the gas diffusion electrode, and a cathode electrode plate is arranged on the side of the gas diffusion electrode away from the membrane electrode, so that the anode and the cathode can be coupled to simultaneously degrade pollutants, improve the degradation efficiency, and no additional supporting electrolyte is needed. The application further provides a parallel structure of the electro-catalytic flow reaction device, which enlarges the working area and improves the pollutant treatment capacity. The application further provides a series structure of the electro-catalytic flow reaction device, which prolongs the treatment time and improves the treatment effect. The application further provides a treatment method, which can deeply treat trace pollutants in sewage through the electro-catalytic flow reaction device.

Description

Technical Field

[0001] This invention belongs to the field of water pollutant degradation. Specifically, this invention relates to an electrocatalytic flow reaction device and its parallel and series structures and treatment methods. Background Technology

[0002] Persistent organic pollutants (POPs), endocrine disruptors, antibiotics, and other trace pollutants have emerged as a new class of environmental pollutants. Due to the difficulty in detecting, accumulating, and degrading these trace pollutants, they are present in water bodies extensively and over a long period. Numerous studies have confirmed that long-term exposure to these low concentrations of trace pollutants can cause harm. Various treatment technologies have been attempted and applied to remove these trace pollutants. Electrochemical catalytic oxidation technology, due to its advantages of being green, efficient, having a high oxidation depth, and being easy to operate, has become a very promising technology for treating organic wastewater.

[0003] When treating pollutant wastewater using electrocatalysis, existing electrochemical reactors require the reaction medium to have good conductivity. Therefore, the reaction system must contain a certain concentration of supporting electrolyte. However, the additional addition of electrolyte to wastewater limits the application scope of electrocatalytic degradation of wastewater. For example, because drinking water or surface water has very poor conductivity, it is difficult to remove pollutants directly by electrocatalysis. The added supporting electrolyte not only increases the treatment cost but also inevitably leads to secondary pollution. Summary of the Invention

[0004] This invention addresses the aforementioned problems and aims to provide an electrocatalytic flow reaction device and its parallel / series structures and treatment methods capable of deep treatment of trace pollutants in water, requiring no additional supporting electrolyte, avoiding secondary pollution, and reducing treatment costs. To achieve the above objectives, the technical solution adopted by this invention is as follows:

[0005] The present invention provides an electrocatalytic flow reaction device, characterized by comprising a membrane electrode and a gas diffusion electrode, wherein a liquid outlet plate is disposed between the membrane electrode and the gas diffusion electrode, an anion exchange membrane is disposed between the liquid outlet plate and the gas diffusion electrode, an anode plate is disposed on the side of the membrane electrode away from the gas diffusion electrode, and a cathode plate is disposed on the side of the gas diffusion electrode away from the membrane electrode.

[0006] The electrocatalytic flow reaction device provided by the present invention may also have the following feature: a first gasket is provided between the anode plate and the liquid outlet plate, and a second gasket is provided between the cathode plate and the liquid outlet plate.

[0007] The electrocatalytic flow reaction device provided by the present invention may also have the following features: an inlet and a first outlet are provided on the anode plate, a second outlet is provided on the liquid outlet plate, and an inlet and an outlet are provided on the cathode plate.

[0008] The electrocatalytic flow reaction device provided by the present invention may also have the following feature: the electrocatalytic membrane material used in the membrane electrode is composed of one or more of inorganic ceramic membranes or three-dimensional porous membranes of metals.

[0009] The electrocatalytic flow reaction apparatus provided by the present invention may also have the feature that the gas diffusion electrode comprises an electro-Fenton catalyst supported on hydrophobic carbon paper.

[0010] The present invention also provides a parallel structure of an electrocatalytic flow reaction device, characterized by comprising the above-mentioned electrocatalytic flow reaction device, wherein at least two sets of cathode plates and anode plates of the electrocatalytic flow reaction device are connected in parallel.

[0011] The present invention also provides a series structure of an electrocatalytic flow reaction device, characterized in that it includes the above-mentioned electrocatalytic flow reaction device, the series structure includes at least two sets of electrocatalytic flow reaction devices, and the outlet and inlet of the two anode plates of the electrocatalytic flow reaction devices are connected.

[0012] In the series structure of the electrocatalytic flow reaction device provided by the present invention, it may also have the following feature: an insulating pad is provided between the electrocatalytic flow reaction devices, and the insulating pad separates the adjacent anode plate and cathode plate.

[0013] This invention also provides a treatment method for treating trace pollutants in water using the aforementioned electrocatalytic flow reaction device, characterized by the following steps: Step S1, starting the electrocatalytic flow reaction device, the membrane electrode is connected to the positive terminal of an external power supply via conductive tape or wire as the anode working electrode, and the gas diffusion electrode is connected to the negative terminal of the external power supply via conductive tape or wire as the cathode counter electrode; Step S2, a peristaltic pump pumps wastewater containing pollutants into the electrocatalytic flow reaction device, the wastewater passes through the membrane electrode, and the pollutants in the water are initially degraded by direct or indirect oxidation through the membrane electrode, and oxygen passes through the gas diffusion electrode, where oxygen is reduced to hydrogen peroxide ions and passes through the anion exchange membrane under the action of an electric field to enter the outlet plate, where it combines with the protons generated by anodic oxidation to produce hydrogen peroxide, which further reacts with the pollutants in the outlet plate to degrade the pollutants.

[0014] The technical advantages of this invention are as follows: The electrocatalytic flow reaction device provided by this invention includes a membrane electrode and a gas diffusion electrode. A liquid outlet plate is provided between the membrane electrode and the gas diffusion electrode, and an anion exchange membrane is provided between the liquid outlet plate and the gas diffusion electrode. An anode plate is provided on the side of the membrane electrode away from the gas diffusion electrode, and a cathode plate is provided on the side of the gas diffusion electrode away from the membrane electrode. This allows for simultaneous degradation of pollutants by coupling the anode and cathode, improving degradation efficiency without the need for additional supporting electrolyte. This invention also provides a parallel structure for the electrocatalytic flow reaction device, expanding the working area and increasing the pollutant treatment capacity. Furthermore, this invention provides a series structure for the electrocatalytic flow reaction device, extending the treatment time and improving the treatment effect. Finally, this invention provides a treatment method capable of deeply treating trace pollutants in wastewater using an electrocatalytic flow reaction device.

[0015] Therefore, the electrocatalytic flow reaction device, its parallel and series structures, and the treatment method provided by this invention can deeply treat trace pollutants in water, without the need for additional supporting electrolytes, thus avoiding secondary pollution and reducing treatment costs. Attached Figure Description

[0016] This manual includes the following figures, which illustrate the following:

[0017] Figure 1 This is an exploded view of the electrocatalytic flow reaction apparatus in an embodiment of the present invention;

[0018] Figure 2 This is a schematic diagram of the anode plate structure in an embodiment of the present invention;

[0019] Figure 3 This is a schematic diagram of the cathode plate structure in an embodiment of the present invention;

[0020] Figure 4 This is an exploded view of the parallel structure of the electrocatalytic flow reaction device in an embodiment of the present invention;

[0021] Figure 5 This is an exploded view of the series structure of the electrocatalytic flow reaction device in an embodiment of the present invention;

[0022] Figure 6 This is a performance diagram of the electrocatalytic flow reaction device used for the electrocatalytic degradation of ciprofloxacin solution in an embodiment of the present invention;

[0023] Figure 7 This is a performance diagram of the parallel structure of the electrocatalytic flow reaction device in an embodiment of the present invention for the electrocatalytic degradation of estriol solution;

[0024] Figure 8 This is a performance diagram of the series structure of the electrocatalytic flow reaction device in an embodiment of the present invention for the electrocatalytic degradation of estriol solution.

[0025] The markings in the diagram are as follows: 10-membrane electrode, 20-gas diffusion electrode, 30-liquid outlet plate, 31-second water outlet, 40-anion exchange membrane, 50-anode plate, 51-water inlet, 52-first water outlet, 60-cathode plate, 61-air inlet, 62-air outlet, 70-first gasket, 80-second gasket, 90-insulating pad. Detailed Implementation

[0026] The specific embodiments of the present invention will be further described in detail below with reference to the accompanying drawings, in order to help those skilled in the art to have a more complete, accurate and in-depth understanding of the inventive concept and technical solution of the present invention, and to facilitate its implementation.

[0027] Figure 1 This is an exploded view of the electrocatalytic flow reaction apparatus in an embodiment of the present invention.

[0028] like Figure 1 As shown, the electrocatalytic flow reaction device provided by the present invention includes a membrane electrode 10 and a gas diffusion electrode 20. A liquid outlet plate 30 is provided between the membrane electrode 10 and the gas diffusion electrode 20. An anion exchange membrane 40 is provided between the liquid outlet plate 30 and the gas diffusion electrode 20. An anode plate 50 is provided on the side of the membrane electrode 10 away from the gas diffusion electrode 20 and is connected to the membrane electrode 10. A cathode plate 60 is provided on the side of the gas diffusion electrode 20 away from the membrane electrode 10 and is connected to the gas diffusion electrode 20. The membrane electrode 10 and the gas diffusion electrode 20 are connected through the anion exchange membrane 40.

[0029] Figure 2 This is a schematic diagram of the anode plate structure in an embodiment of the present invention; Figure 3 This is a schematic diagram of the cathode plate in an embodiment of the present invention.

[0030] like Figure 2 and Figure 3 As shown, the anode plate 50 is provided with a water inlet 51 and a first water outlet 52, and the cathode plate 60 is provided with an air inlet 61 and an air outlet 62. The liquid outlet plate 30 is provided with a second water outlet 31, which is connected to the water inlet 51.

[0031] A first gasket 70 is provided between the anode plate 50 and the liquid outlet plate 30, and a second gasket 80 is provided between the cathode plate 60 and the liquid outlet plate 30. The first gasket 70 prevents water leakage at the membrane electrode 10, and the second gasket 80 prevents water leakage at the gas diffusion electrode 20, thus avoiding affecting the treatment effect of trace pollutants. The first gasket 70 and the second gasket 80 are fluororubber gaskets.

[0032] The membrane electrode 10 uses an electrocatalytic membrane material composed of one or more of inorganic ceramic membranes or three-dimensional porous membranes of metals. The gas diffusion electrode 20 includes an electro-Fenton catalyst supported on hydrophobic carbon paper. The membrane electrode 10 is connected to the positive terminal of an external power supply via conductive tape or wires, serving as the anode working electrode. The gas diffusion electrode 20 is connected to the negative terminal of the external power supply via conductive tape or wires, serving as the cathode counter electrode. The anion exchange membrane 40 can unidirectionally transfer the oxide anions generated at the gas diffusion electrode 20 to the membrane electrode 10. The anion exchange membrane 40 can also prevent reverse reactions and short circuits, thereby avoiding the need to add additional supporting electrolytes, preventing secondary pollution, and reducing wastewater treatment costs.

[0033] The operating voltage of the electrocatalytic flow reactor is 1.5V-2.5V, and the treatment time for wastewater by the electrocatalytic flow reactor is 10min-60min.

[0034] Figure 4 This is an exploded view of the parallel structure of the electrocatalytic flow reaction device in an embodiment of the present invention.

[0035] like Figure 4 As shown, the present invention also provides a parallel structure for an electrocatalytic flow reaction device, wherein at least two sets of cathode plates 60 and anode plates 50 of the electrocatalytic flow reaction device are connected in parallel. The parallel structure of the electrocatalytic flow reaction device can expand the working area and increase the pollutant treatment capacity.

[0036] Figure 5 This is an exploded view of the series structure of the electrocatalytic flow reaction device in an embodiment of the present invention;

[0037] like Figure 5 As shown, the present invention also provides a series structure of electrocatalytic flow reaction devices. The series structure of electrocatalytic flow reaction devices includes at least two sets of electrocatalytic flow reaction devices. The inlet and outlet of the electrocatalytic flow reaction devices are connected. In two adjacent sets of electrocatalytic flow reaction devices, the first outlet 52 of one set of electrocatalytic flow reaction devices is connected to the inlet 51 of the other set of electrocatalytic flow reaction devices. An insulating pad 90 is provided between the two adjacent sets of electrocatalytic flow reaction devices. The series structure of electrocatalytic flow reaction devices can extend the treatment time and improve the deep treatment effect of trace pollutants.

[0038] The present invention also provides a processing method, comprising the following steps:

[0039] Step S1: Start the electrocatalytic flow reaction device. The membrane electrode 10 is connected to the positive terminal of the external power supply via conductive tape or wire, serving as the anode working electrode. The gas diffusion electrode 20 is connected to the negative terminal of the external power supply via conductive tape or wire, serving as the cathode counter electrode.

[0040] In step S2, a peristaltic pump pumps wastewater containing pollutants into the electrocatalytic flow reactor through inlet 51. The wastewater is first discharged through the first outlet 52 to purge air from the reactor, then the first outlet 52 is closed, allowing the wastewater to flow to the second outlet 31. The wastewater passes through the membrane electrode 10, where it undergoes direct or indirect oxidation to initially degrade the pollutants. Oxygen enters the electrocatalytic flow reactor through inlet 61 and exits through outlet 62. As oxygen passes through the gas diffusion electrode 20, it is reduced to hydrogen peroxide ions, which, under the influence of an electric field, pass through the anion exchange membrane 40 and enter the effluent plate 30. There, hydrogen peroxide combines with superoxide radicals and hydroxyl radicals generated at the membrane electrode 10 to produce hydrogen peroxide. This hydrogen peroxide further oxidizes the pollutants within the effluent plate 30, further degrading them. The deeply treated wastewater is then discharged from the second outlet 31.

[0041] Figure 6 This is a performance diagram of the electrocatalytic flow reaction device used for the electrocatalytic degradation of ciprofloxacin solution in an embodiment of the present invention;

[0042] like Figure 6 As shown, the process of deep treatment of ciprofloxacin (CIP) in wastewater using the electrocatalytic flow reaction device provided by this invention includes the following steps:

[0043] Step 1: Start the electrocatalytic flow reaction apparatus. Membrane electrode 10 is connected to the positive terminal of the external power supply via conductive tape or wire, serving as the anode working electrode. Gas diffusion electrode 20 is connected to the negative terminal of the external power supply via conductive tape or wire, serving as the cathode counter electrode. The external power supply is an electrochemical workstation with a working voltage of 2V.

[0044] Step 2: A peristaltic pump pumps wastewater containing pollutants into the electrocatalytic flow reactor through inlet 51. The wastewater flow rate is 1 mL / min. It is first discharged through the first outlet 52 to purge the air from the electrocatalytic flow reactor, then the first outlet 52 is closed, allowing the wastewater to flow to the second outlet 31. The wastewater passes through the membrane electrode 10, where it undergoes direct or indirect oxidation to initially degrade the pollutants. Oxygen enters the electrocatalytic flow reactor through inlet 61 and passes through the gas diffusion electrode 20. The gas diffusion electrode 20 reduces oxygen to hydrogen peroxide ions, which, under the influence of an electric field, pass through the anion exchange membrane 40 and enter the outlet plate 30. There, they combine with superoxide radicals generated at the membrane electrode 10 to produce hydrogen peroxide, which further oxidizes and degrades the pollutants within the outlet plate 30. The deeply treated wastewater is then discharged from the second outlet 31. By applying different voltages and measuring the concentrations of various pollutants after degradation using high-performance liquid chromatography, the degradation rate of ciprofloxacin can reach over 90% at a working voltage of 2V.

[0045] Figure 7 This is a performance diagram of the parallel structure of the electrocatalytic flow reaction device in an embodiment of the present invention for the electrocatalytic degradation of estriol solution.

[0046] like Figure 7 As shown, the process of deep treatment of estriol solution (E3) in wastewater using the parallel structure of the electrocatalytic flow reaction device provided by the present invention includes the following steps:

[0047] Step 1: Start the electrocatalytic flow reaction apparatus. Membrane electrode 10 is connected to the positive terminal of the external power supply via conductive tape or wire, serving as the anode working electrode. Gas diffusion electrode 20 is connected to the negative terminal of the external power supply via conductive tape or wire, serving as the cathode counter electrode. The external power supply is an electrochemical workstation with a working voltage of 2V.

[0048] Step 2: A peristaltic pump pumps wastewater containing pollutants into the electrocatalytic flow reactor through inlet 51. The wastewater flow rate is 1 mL / min. It is first discharged through the first outlet 52 to purge the air from the electrocatalytic flow reactor, then the first outlet 52 is closed, allowing the wastewater to flow to the second outlet 31. The wastewater passes through the membrane electrode 10, where it undergoes direct or indirect oxidation to initially degrade the pollutants. Oxygen enters the electrocatalytic flow reactor through inlet 61 and passes through the gas diffusion electrode 20. The gas diffusion electrode 20 reduces oxygen to hydrogen peroxide ions, which, under the influence of an electric field, pass through the anion exchange membrane 40 and enter the outlet plate 30. There, they combine with superoxide radicals generated at the membrane electrode 10 to produce hydrogen peroxide, which further oxidizes and degrades the pollutants within the outlet plate 30. The deeply treated wastewater is then discharged from the second outlet 31. By applying different voltages and measuring the concentrations of various pollutants after degradation using high-performance liquid chromatography, the degradation rate of estriol can reach over 90% at a working voltage of 2V.

[0049] Figure 8 This is a performance diagram of the series structure of the electrocatalytic flow reaction device in an embodiment of the present invention for the electrocatalytic degradation of estriol solution.

[0050] like Figure 8 As shown, the process of deep treatment of estriol solution (E3) in wastewater using the series structure of the electrocatalytic flow reaction device provided by the present invention includes the following steps:

[0051] Step 1: Start the electrocatalytic flow reaction apparatus. Membrane electrode 10 is connected to the positive terminal of the external power supply via conductive tape or wire, serving as the anode working electrode. Gas diffusion electrode 20 is connected to the negative terminal of the external power supply via conductive tape or wire, serving as the cathode counter electrode. The external power supply is an electrochemical workstation with a working voltage of 2V.

[0052] Step 2: A peristaltic pump pumps wastewater containing pollutants into the electrocatalytic flow reactor through inlet 51. The wastewater flow rate is 1 mL / min. It is first discharged through the first outlet 52 to purge the air from the electrocatalytic flow reactor, then the first outlet 52 is closed, allowing the wastewater to flow to the second outlet 31. The wastewater passes through the membrane electrode 10, where it undergoes direct or indirect oxidation to initially degrade the pollutants. Oxygen enters the electrocatalytic flow reactor through inlet 61 and passes through the gas diffusion electrode 20. The gas diffusion electrode 20 reduces oxygen to hydrogen peroxide ions, which, under the influence of an electric field, pass through the anion exchange membrane 40 and enter the outlet plate 30. There, they combine with superoxide radicals generated at the membrane electrode 10 to produce hydrogen peroxide, which further oxidizes and degrades the pollutants within the outlet plate 30. The deeply treated wastewater is then discharged from the second outlet 31. By applying different voltages and measuring the concentrations of various pollutants after degradation using high-performance liquid chromatography, the degradation rate of estriol can reach over 100% at a working voltage of 2V.

[0053] Therefore, the electrocatalytic flow reaction device and its parallel, series, and treatment methods provided by this invention can deeply treat trace pollutants in water, without the need for additional supporting electrolytes, avoiding secondary pollution and reducing treatment costs.

[0054] The role and effect of the embodiments

[0055] The electrocatalytic flow reaction device provided by this invention includes a membrane electrode 10 and a gas diffusion electrode 20. A liquid outlet plate 30 is disposed between the membrane electrode 10 and the gas diffusion electrode 20. An anion exchange membrane 40 is disposed between the liquid outlet plate 30 and the gas diffusion electrode 20. An anode plate 50 is disposed on the side of the membrane electrode 10 away from the gas diffusion electrode 20, and a cathode plate 60 is disposed on the side of the gas diffusion electrode 20 away from the membrane electrode 10. This device can simultaneously degrade pollutants by coupling the anode and cathode, improving degradation efficiency without the need for additional supporting electrolyte. This invention also provides a parallel structure for the electrocatalytic flow reaction device, expanding the working area and increasing the pollutant treatment capacity. This invention also provides a series structure for the electrocatalytic flow reaction device, extending the treatment time and improving the treatment effect. This invention also provides a treatment method that can deeply treat trace pollutants in wastewater using an electrocatalytic flow reaction device. The electrocatalytic flow reaction device, its parallel and series structures, and the treatment method provided by this invention can deeply treat trace pollutants in water without the need for additional supporting electrolyte, avoiding secondary pollution and reducing treatment costs.

[0056] The present invention has been described above by way of example with reference to the accompanying drawings. Obviously, the specific implementation of the present invention is not limited to the above-described manner. Any non-substantial improvements made using the inventive concept and technical solution; or the direct application of the inventive concept and technical solution to other situations without modification, are all within the protection scope of the present invention.

Claims

1. An electrocatalytic flow reaction apparatus, characterized in that, The device includes a membrane electrode (10) and a gas diffusion electrode (20). A liquid outlet plate (30) is provided between the membrane electrode (10) and the gas diffusion electrode (20). An anion exchange membrane (40) is provided between the liquid outlet plate (30) and the gas diffusion electrode (20). An anode plate (50) is provided on the side of the membrane electrode (10) away from the gas diffusion electrode (20), and a cathode plate (60) is provided on the side of the gas diffusion electrode (20) away from the membrane electrode (10). An inlet (51) and a first outlet (52) are provided on the anode plate (50), and a second outlet is provided on the liquid outlet plate (30). (31) The cathode plate (60) is provided with an air inlet (61) and an air outlet (62), and at least two sets of cathode plates (60) and anode plates (50) of electrocatalytic flow reaction devices are connected in parallel; or, at least two sets of electrocatalytic flow reaction devices, the outlet and inlet of the two anode plates (50) of the electrocatalytic flow reaction devices are connected, an insulating pad (90) is provided between the electrocatalytic flow reaction devices, the insulating pad (90) separates the adjacent anode plates (50) and cathode plates (60), and the first outlet (52) of one set of electrocatalytic flow reaction devices is connected to the inlet (51) of another set of electrocatalytic flow reaction devices.

2. The electrocatalytic flow reaction apparatus according to claim 1, characterized in that, A first gasket (70) is provided between the anode plate (50) and the liquid outlet plate (30), and a second gasket (80) is provided between the cathode plate (60) and the liquid outlet plate (30).

3. The electrocatalytic flow reaction apparatus according to claim 2, characterized in that, The electrocatalytic membrane material used in the membrane electrode (10) is composed of one or more of inorganic ceramic membranes or three-dimensional porous membranes of metals.

4. The electrocatalytic flow reaction apparatus according to claim 3, characterized in that, The gas diffusion electrode (20) comprises an electro-Fenton catalyst supported on hydrophobic carbon paper.

5. A method for treating trace pollutants in water using the electrocatalytic flow reaction apparatus according to any one of claims 1 to 4, characterized in that, Includes the following steps: Step S1: Start the electrocatalytic flow reaction device. The membrane electrode (10) is connected to the positive terminal of the external power supply via conductive tape or wire, serving as the anode working electrode. The gas diffusion electrode (20) is connected to the negative terminal of the external power supply via conductive tape or wire, serving as the cathode counter electrode. Step S2: The peristaltic pump pumps the sewage containing pollutants into the electrocatalytic flow reaction device. The sewage passes through the membrane electrode (10), which directly or indirectly oxidizes and initially degrades the pollutants in the water. Oxygen passes through the gas diffusion electrode (20), which reduces oxygen to hydrogen peroxide ions and passes through the anion exchange membrane into the outlet plate (30) under the action of an electric field. The hydrogen peroxide ions combine with the protons generated by the anodic oxidation to produce hydrogen peroxide. The hydrogen peroxide ions further react with the pollutants in the outlet plate (30) to degrade the pollutants.

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