Electrochemical water treatment device for coupling porous titanium black oxidation with cathode oxygen reduction

Abstract

The utility model discloses an electrochemical water treatment device for coupling porous titanium black oxidation with cathode oxygen reduction. Comprising a box body, a water inlet, a water inlet storage tank, a porous water distribution plate, a sintered porous titanium black anode, a porous cathode, an overflow water outlet tank, a water outlet, a return pipe, a gas-liquid mixing pump, a gas-liquid mixing main conveying pipe, a gas-liquid mixing conveying branch pipe and a microbubble generator. By adopting the mode, the electrochemical water treatment device for coupling porous titanium black oxidation with cathode oxygen reduction has the advantages that in the electrochemical water treatment process, the oxygen content in wastewater is increased by utilizing microbubble aeration, and the cathode reaction potential can be greatly reduced by utilizing a cathode oxygen reduction reaction to replace a water decomposition hydrogen production reaction; wastewater penetrates through the porous electrode to compress the mass transfer distance of pollutants diffused to the surface of the electrode, so that the overall pollutant degradation capacity of the device is improved, and the water treatment energy consumption of the system is reduced.

Description

TECHNICAL FIELD

[0001] The utility model belongs to the field of water quality electrochemistry water treatment, especially relates to a kind of porous titanium suboxide anodic oxidation coupling cathode oxygen reduction electrochemical water treatment device. BACKGROUND

[0002] Electrochemical water treatment technology is an important method for treating refractory organic pollutant wastewater in the field of industrial water treatment, which has the advantages of fast reaction rate, good pollutant mineralization effect, small occupation area, easy reaction control, etc.Electrochemical water treatment device generally includes power supply, electrolytic tank box, anode, cathode, etc.In the electrolytic tank box of electrochemical water treatment, electrode plates are usually arranged in parallel, and water flow adopts ordinary push flow mode of deflection or overflow.Anode generally uses catalytic materials with high oxygen evolution overpotential, such as PbO2, SnO2, Ti4O7, etc., which oxidizes pollutants directly or generates hydroxyl radicals to oxidize pollutants indirectly.Cathode usually uses stainless steel, titanium and other materials, and mainly generates hydrogen evolution reaction.On the one hand, hydrogen generated by cathode evolution reaction is explosive (explosion limit 4.0~75.6%, volume concentration), and exhaust system needs to be set to discharge hydrogen in time to prevent accumulation;On the other hand, the potential required for hydrogen evolution reaction is high, and the theoretical hydrogen production potential is 0V (compared with reversible hydrogen electrode), and the extra energy consumption of cathode is not negligible due to reaction overpotential.

[0003] In terms of electrode structure, the existing electrode is generally a plate electrode prepared by taking a metal plate as a substrate, and the surface of the electrode plate is coated with an electrocatalyst.Reaction substances usually reach the electrode surface interface by diffusion to occur oxidation reaction, and the lifetime of key oxidizing species such as free radicals is short, so that the anode has poor degradation performance for pollutants far away from the electrode surface, and the related water treatment effect needs to be further improved. UTILITY MODEL CONTENTS

[0004] To solve the above technical problems, the utility model aims to provide a kind of electrochemical water treatment device of porous titanium suboxide oxidation coupling cathode oxygen reduction, comprising: tank, water inlet, water storage tank, porous water distribution plate, sintered porous titanium suboxide anode, porous cathode, overflow water tank, water outlet, reflux pipe, gas-liquid mixing pump, gas-liquid mixing main delivery pipe, gas-liquid mixing delivery branch pipe and micro-bubble generator structure.

[0005] The tank is provided with a limiting slot, the sintered porous titanium suboxide anode and the porous cathode are arranged in parallel in the limiting slot of the tank, a fixed gap is provided between the sintered porous titanium suboxide anode and the porous cathode, and a micro-bubble generator for injecting reflux gas-liquid mixed water is provided between the gaps;The porous titanium suboxide anode and the porous cathode can make water flow through the electrode plate.

[0006] The present invention relates to an electrochemical water treatment device for oxygen reduction by a porous titanium suboxide oxidation coupled cathode. The porous titanium suboxide anode has the ability to directly or indirectly oxidize pollutants in water; the porous cathode can undergo an oxygen reduction reaction under power supply.

[0007] The present invention describes an electrochemical water treatment device for porous sub-titanium oxide oxidation coupled to cathode oxygen reduction, which uses a gas-liquid mixing pump to pump the gas and the treated water overflowing from the water tank back to the electrode reaction zone.

[0008] The present invention discloses an electrochemical water treatment device for porous titanium suboxide oxidation coupled to cathode oxygen reduction. The microbubble generator injects liquid rich in microbubbles into the electrolytic cell, providing liquid disturbance, rinsing the electrode plates, increasing dissolved oxygen in the water, and removing harmful or dangerous gases generated by the electrode reaction.

[0009] The present invention discloses an electrochemical water treatment device for porous titanium suboxide oxidation coupled to cathode oxygen reduction. The device has a reflux system, and the reflux ratio can be adjusted according to the treatment effect to carry out continuous flow reaction or sequential batch reaction.

[0010] The present invention relates to an electrochemical water treatment device for a porous sub-titanium oxide oxidation coupled to a cathode oxygen reduction, wherein the front end of the tank inlet has a porous water distribution structure and the rear end overflow outlet has a collection structure.

[0011] The beneficial effects of this invention are: increasing the oxygen content in wastewater through microbubble aeration; significantly reducing the cathode reaction potential by replacing the water decomposition hydrogen production reaction with the cathode oxygen reduction reaction, thereby reducing the voltage between the anode and cathode plates of the electrolyzer; compressing the mass transfer distance of pollutants to the electrode surface by utilizing the penetration of wastewater through porous electrodes, while simultaneously enhancing the reaction process of pollutant degradation by the oxidative free radicals generated at the anode through the confinement effect of the pore structure; and improving the overall pollutant degradation capacity of the electrolyzer and reducing the energy consumption of water treatment in the electrolyzer under the combined effect of the above effects. Attached Figure Description

[0012] To more clearly illustrate the technical solutions in the embodiments of this utility model, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only one embodiment of this utility model. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort, wherein:

[0013] Figure 1 This is a schematic diagram of a preferred embodiment of an electrochemical water treatment device for porous sub-titanium oxide oxidation coupled to cathode oxygen reduction according to this utility model.

[0014] Figure 2This is a front view schematic diagram of the porous titanium suboxide anode plate and slot of a porous titanium suboxide oxidation coupled cathode oxygen reduction electrochemical water treatment device of this utility model;

[0015] Among them, 1-box body; 1a-groove for embedding electrodes on the box body; 2-water inlet; 3-water inlet storage tank; 4-porous water distribution plate; 5a, 5b-sintered porous sub-titanium oxide anode; 6a, 6b-porous cathode; 7-overflow water tank; 8-water outlet; 9-return pipe; 10-gas-liquid mixing pump; 11-gas-liquid mixing main conveying pipe; 12-gas-liquid mixing conveying branch pipe; 13-microbubble generator. Detailed Implementation

[0016] The technical solutions in the embodiments of this utility model will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of this utility model, and not all of them, and are intended to provide further explanation of this utility model. Unless otherwise specified, all technical and scientific terms used in this utility model have the same meaning as commonly understood by those skilled in the art to which this utility model pertains.

[0017] The present invention will be further described below with reference to embodiments:

[0018] like Figure 1 , Figure 2 As shown, the electrochemical water treatment device based on porous sub-titanium oxide oxidation coupled cathode oxygen reduction includes a tank and a slotted 1a fixed electrode, two sets of electrodes, a water distribution and drainage device, and a return microbubble aeration device. During operation, the wastewater to be treated enters the inlet tank (2-inlet) and then the electrode area via the porous distribution plate (4-porous water distribution plate). The porous sub-titanium oxide anode (5a) and porous foam cathode (6a) are placed in parallel, and the second set of parallel electrode plates (5b and 6b) are similarly placed. All electrodes are fixed in the tank via the fixing groove (1a-fixing groove). The anode and cathode are connected to the negative and positive terminals of the power supply via the upper electrode tabs, respectively. The wastewater entering the electrode area via the porous distribution plate (4-porous water distribution plate) can penetrate the porous anode and cathode plates (5a, 6a, 5b, and 6b) under the propulsion of the water flow, and enters the overflow outlet tank (7-overflow weir) via the overflow weir. Partially treated water is discharged through the drain outlet (8-drainage outlet). Partially treated water enters the gas-liquid mixing pump via the return pipe (9-return pipe), mixes with air, and then enters the gas-liquid mixing main delivery pipe (11-gas-liquid mixing main delivery pipe) via the gas-liquid mixing branch pipe (12-gas-liquid mixing branch pipe). It is then injected into the electrode reaction area via the microbubble generator (13-microbubble generator). The microbubble generator is fixed to the bottom of the tank (1-tank).

[0019] The electrochemical water treatment device of porous titanium suboxide oxidation coupled to cathode oxygen reduction according to this utility model includes an electrolytic cell tank, an inlet area, an outlet area, a porous titanium suboxide anode plate, a porous cathode plate, a microbubble aeration device, and a fixing and connecting mechanism. The inlet area and the outlet area are connected on the electrolytic cell tank. The porous titanium suboxide anode plate and the porous cathode plate are fixed in the tank through slots. Water flows naturally through the anode and cathode plates under gravity pressure. The microbubble aeration port is set between the anode and cathode plates at the bottom of the tank. The water flow is disturbed by a gas-liquid mixing pump and a shear microbubble generator, and the water rich in microbubbles is circulated into the electrolytic cell. The fixing and connecting mechanism includes an electrode fixing bracket, a slot, and a microbubble aeration port fixing bracket, etc., to facilitate the assembly and disassembly of the electrode plate and the aeration head.

[0020] In a preferred embodiment of this utility model, the combination of anodic oxidation and cathodic oxygen reduction reaction results in a lower electrolytic cell pressure under the same operating current conditions. The microbubble aeration gas source used is natural air, the flow rate of the return aeration water is controllable, and the air-to-water ratio is adjustable within a certain range.

[0021] In a preferred embodiment of this invention, the use of multiple sets of porous anode and cathode plates has a better single-pass pollutant removal capability. The anode used is a sintered porous sub-titanium oxide electrode, and the cathode is a stainless steel mesh electrode.

[0022] In a preferred embodiment of this invention, the porous titanium suboxide anode surface species are nano-Magnéli phase titanium suboxide, which has good chemical inertness, high oxygen evolution overpotential, and good stability. The porous cathode material is porous foamed titanium. Both the anode and cathode can be prepared by sintering, and the surface and interior have abundant pore structures, which can ensure water flow penetration through the electrodes. The overall system exhibits good pollutant mineralization and removal capabilities and a long electrode life in high-salt organic wastewater treatment scenarios.

[0023] More preferably, the electrode plates arranged inside the box can be multiple sets, not limited to the two sets of parallel anode and cathode plates described in this embodiment.

[0024] More preferably, the porous cathode has the ability to electrocatalyze oxygen reduction reaction, and it can be made of materials such as titanium, stainless steel, nickel, and aluminum.

[0025] More preferably, the porous sub-titanium oxide anode has the ability to electro-oxidize and degrade pollutants, and its material can be replaced with lead oxide, tin oxide, antimony-doped tin oxide, titanium oxide, or porous electrodes composed of the above materials.

[0026] In this embodiment, the reflux aeration device includes 9-reflux pipe, 10-gas-liquid mixing pump, 11-gas-liquid mixing main delivery pipe, 12-gas-liquid mixing delivery branch pipe, and 13-microbubble generator. The reflux water volume is controlled by the pump and valves, and the aeration volume is controlled by the pump inlet flow meter. Through reflux aeration, the dissolved oxygen in the water can be increased to a supersaturated dissolved oxygen state greater than 8 mg / L, so that the cathode mainly undergoes the oxygen reduction reaction. In addition, the excess air can carry the gas generated by the electrochemical reaction out of the electrolytic cell tank, preventing the accumulation of dangerous gases. The horizontal reflux is injected into the electrode plate, which can promote uniform liquid mixing and prevent short-circuiting problems. At the same time, it is beneficial to wash off the material on the electrode surface to prevent the electrode hole structure from being blocked.

[0027] More preferably, the reflux aeration device can be a swirl shear microbubble generator, a variable diameter microbubble generator, or a microporous aeration head; the aeration gas used can be natural air, ozone, etc.

[0028] Through the above-described method, this utility model provides an electrochemical water treatment device with porous sub-titanium oxide oxidation coupled to cathode oxygen reduction. During the electrochemical water treatment process, microbubble aeration is used to increase the oxygen content in the wastewater. The cathode oxygen reduction reaction replaces the water decomposition hydrogen production reaction, which can significantly reduce the cathode reaction potential. By utilizing the wastewater to penetrate the porous electrode, the mass transfer distance of pollutants diffused to the electrode surface is compressed, thereby improving the overall pollutant degradation capacity of the device and reducing the system's water treatment energy consumption.

[0029] The above description is merely an embodiment of this utility model and does not limit the patent scope of this utility model. Any equivalent structural or procedural transformations made using the content of this utility model specification, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of this utility model.

Claims

1. An electrochemical water treatment device for oxidation coupling cathode oxygen reduction by porous titania suboxide, characterized by, It comprises: a box, a water inlet, a water storage tank, a porous water distribution plate, a sintered porous titanium suboxide anode, a porous cathode, an overflow water tank, a water outlet, a reflux pipe, a gas-liquid mixing pump, a gas-liquid mixing main delivery pipe, a gas-liquid mixing delivery branch pipe, and a micro-bubble generator structure. The box is provided with a limiting groove, the sintered porous titanium suboxide anode and the porous cathode are arranged in parallel in the limiting groove of the box, a fixed gap is arranged between the sintered porous titanium suboxide anode and the porous cathode, and a micro-bubble generator for injecting reflux gas-liquid mixed water is arranged between the gaps; the porous titanium suboxide anode and the porous cathode can make water flow through the electrode plates.

2. The electrochemical water treatment device of claim 1, wherein the porous titanium suboxide oxidation coupling cathode is characterized by: The porous titanium suboxide anode has the ability to directly or indirectly oxidize pollutants in water; the porous cathode can undergo oxygen reduction reaction under the drive of a power source.

3. The electrochemical water treatment device of claim 1, wherein the porous titanium suboxide oxidation coupling cathode is characterized by: The gas-liquid mixing pump is used to pump the gas and the water in the overflow water tank after treatment back to the electrode reaction zone.

4. The electrochemical water treatment device of claim 1 or 3, wherein the porous titanium suboxide oxidation coupling cathode is characterized by, The micro-bubble generator injects liquid rich in micro-bubbles into the electrolytic tank, provides liquid disturbance, washes the electrode plates, increases the dissolved oxygen in water, and carries away harmful or dangerous gases generated by the electrode reaction.

5. The electrochemical water treatment device of claim 1, wherein the porous titanium suboxide oxidation coupling cathode is characterized by: The device has a reflux system, and can adjust the reflux proportion to carry out continuous flow reaction or sequencing batch reaction according to the treatment effect.

6. The electrochemical water treatment device of claim 1, wherein the porous titanium suboxide oxidation coupling cathode is characterized by: The box is provided with a porous water distribution structure at the front end of the water inlet and a collection structure at the rear end of the overflow water outlet.

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