CN105293644A - Photoelectrochemical electrolytic equipment and electrode plates for photoelectrochemical electrolytic equipment - Google Patents

Abstract

The invention discloses a photoelectrochemical electrolysis device, which comprises an electrolytic cell, a quartz tube, an ultraviolet lamp and an electrode plate arranged in the electrolytic cell. The surface is coated with a metal oxide coating to form the anode part, and the other half of the surface is coated with a semiconductor photocatalyst coating to form the cathode part. There is an anode part between the two cathode parts, and an insulation is provided between the two electrode plates. spacers, and the electrode plates are connected in series through insulating support rods, the quartz tubes stand upright through the electrode plates, and the upper ends of the quartz tubes pass upwards out of the electrolytic cell. Compared with the existing technology, it can make the ultraviolet photochemical oxidation, photocatalytic oxidation and electrocatalytic oxidation treatment technology have a synergistic effect, so that the whole degradation process of sewage is rapid, efficient, simple in structure, easy to maintain, easy to disassemble and assemble, The advantage of low production cost. The invention also discloses an electrode plate used in the photoelectrochemical electrolysis device.

Description

Photoelectrochemical electrolysis device and electrode plate used in the photoelectrochemical electrolysis device

technical field

The invention relates to a sewage treatment device, in particular to a photoelectrochemical electrolysis device which integrates photochemical oxidation technology, photocatalytic oxidation technology and electrocatalytic oxidation technology to form a synergistic effect.

Background technique

Worldwide environmental pollution and ecological damage have caused people to pay great attention to high-efficiency, energy-saving, and non-secondary pollution environmental governance technologies. In recent years, photocatalytic oxidation technology and electrocatalytic oxidation technology have attracted continuous attention from scholars at home and abroad as treatment methods for toxic or refractory organic pollutants. These two technologies have simple structure, easy control of operating conditions, and oxidation capacity Strong, no secondary pollution and other advantages, become the two most active research hotspots in the field of environmental pollution control, and show broad application prospects.

Photocatalytic technology is the process of using light energy to decompose pollutants into non-toxic or less toxic substances under the action of semiconductor photocatalysts. The basic principle is: when the semiconductor photocatalyst is irradiated by light with energy greater than the forbidden band width, the electrode on the valence band is excited, crosses the forbidden band and enters the conduction band, leaving positively charged holes on the valence band. Holes are extremely oxidizing, and can capture electrons in water to produce highly oxidizing hydroxyl radicals. Hydroxyl radicals can non-selectively oxidize organic pollutants near the electrode surface, and can produce the so-called "electrical The chemical combustion” process completely oxidizes organic matter into CO ₂ and water; but in practical applications, the photocatalytic oxidation process needs to be fed with an electron capture agent to capture photogenerated electrons, so as to effectively and rapidly oxidize and degrade organic matter. The commonly used electron capture agent is oxygen.

From an engineering point of view, photocatalytic treatment of organic wastewater usually uses two reaction systems:

One is the suspended photocatalyst water treatment system, which is to disperse the powdery photocatalyst material in the sewage, and then apply light radiation. Because the photocatalyst has a large contact area with organic pollutants, it shows good photocatalytic oxidation efficiency. In most cases Organic matter can be completely mineralized. However, the suspension phase powder material has disadvantages such as difficult recovery and easy poisoning; these disadvantages make it difficult for this system to become a practical technology.

The other is the immobilization system, which is to cure the photocatalyst on a suitable carrier and then apply light radiation. This system can also improve the efficiency of the photocatalytic reaction by means of an external electric field; the principle is: in the photocatalytic system, the external electric field can be A potential gradient is generated inside the photoelectrode, so that the photogenerated electrons migrate to the counter electrode under the action of the electric field, the carriers are separated, and the recombination of "electron-holes" is reduced, so that a high hole concentration can be maintained in the semiconductor , which is beneficial to give full play to the oxidation of photogenerated holes, thereby improving the efficiency of photocatalytic reactions. The immobilization technology overcomes the disadvantage that the photocatalyst is difficult to recover in the suspension phase system, and uses an external electric field to suppress the simple recombination of "electron-hole", which is relatively more practical. However, issues such as the quantum effect and the weakening of the surface and interface effects caused by the reduction of the specific surface area of the supported catalyst are still unresolved.

Electrocatalytic technology refers to a kind of catalysis that accelerates the charge transfer reaction on the electrode and electrolyte interface under the action of an external electric field. The selected electrode material has a catalytic effect during the electrification process, thereby changing the electrode reaction rate or reaction direction. And it does not undergo qualitative changes; that is, the electrocatalysis includes two aspects of electrode reaction and catalysis, so the electrocatalysis electrode must have these two functions at the same time: ① can conduct electricity and transfer electrons relatively freely; ② can react to the reaction substrate for efficient catalytic activation.

In the electrocatalytic process, the precipitation of oxygen at the anode must be avoided. In the single electrocatalytic oxidation degradation of organic matter, the precipitation of oxygen is considered as a side reaction, which is a waste of electric energy; because the oxidation ability of the oxygen electrolytically separated from the anode is far inferior to that of hydroxyl radicals , hydrogen peroxide and ozone, therefore, most of the oxygen precipitated from the anode is precipitated into the air, which is equal to a waste of electric energy. In order to suppress the occurrence of oxygen evolution side reactions, electrode materials with high oxygen evolution overpotential are usually used, such as tin dioxide/titanium-based anodes without electrocatalytic activity, lead dioxide anodes, or boron-doped diamond electrode materials; this Such materials have a high oxygen evolution overpotential, so they can effectively reduce the occurrence of oxygen evolution side reactions and improve the electrolysis efficiency. However, the use of anodes of this type of material leads to high cell pressure, and the actual energy consumption is still very high, so the problem of energy consumption has not been fundamentally solved. In addition, electrocatalysis is mainly to degrade organic matter into small molecular organic matter, and it is difficult to completely degrade organic matter into carbon dioxide and water.

Photochemical oxidation is also commonly used as an organic wastewater treatment method. Photochemical oxidation is a chemical reaction that occurs under the action of light. Photochemical reactions require organic molecules to absorb electromagnetic radiation of a specific wavelength, to be excited, to generate molecular excited states, and then to undergo chemical changes to another stable state, or to become intermediate chemical products that trigger thermal reactions. Photochemical oxidation technology has the following deficiencies: (1) Under the irradiation of ultraviolet light, some organic substances can be directly decomposed into small molecular organic substances or carbon dioxide and water, but it is only effective for a small part of organic substances, and the efficiency of photodegradation of organic substances is low (2) Usually, photochemical oxidation technology needs to add ozone, hydrogen peroxide, etc. as oxidants, and hydrogen peroxide can be transformed into hydroxyl radicals with stronger oxidation performance under ultraviolet light irradiation, so that pollutants can be oxidized and decomposed under ultraviolet light irradiation .

To sum up, each method has certain limitations when used alone. Therefore, how to apply various oxidation technologies together and form a synergistic effect to ensure the effect of water quality treatment is the current research direction for refractory organic wastewater treatment.

Devices that adopt photochemical oxidation and electrocatalytic oxidation synergistic treatment have appeared in the market, such as the Chinese invention patent, the publication number of which was published on February 25, 2004 is the technology and device of photoelectric synergy and efficient purification of drinking water of CN1477061A, which includes Integrated photolysis and electrolysis integrated reactor, ultraviolet lamp, inner cylinder as the mesh material of the electrolysis positive plate and the outer cylinder of the reactor as the electrolysis cathode, the photolysis of the ultraviolet light emitted by the ultraviolet lamp The combined effect of electrolysis and electrode electrolysis can quickly and effectively degrade organic pollutants in water by producing a synergistic water purification effect. Yet, show through experiment, this device is still unsatisfactory to the treatment effect of sewage; As can be seen from embodiment two, this device is all lower to the removal rate of organic carbon and to the treatment effect of pentachlorophenol; Due to the limitation of the overall structure, there are several technical problems as follows: (1) With the structure of a cylinder inside a cylinder, the area of the anode that can be illuminated in a single electrolytic cell is limited, only the inner surface of the cylindrical anode; (2) The anode material selected is a material with a single function, such as ruthenium dioxide/titanium-based electrodes, lead dioxide/titanium-based electrodes are electrocatalytic anodes, which do not have photocatalytic activity; titanium dioxide/titanium-based electrodes are inert electrodes, which have photocatalytic properties , without electrocatalytic activity; (3) the cathode adopts stainless steel or graphite material, which has no photocatalytic performance; therefore, the treatment effect of the device disclosed in the patent of CN1477061A is slightly worse.

In view of this, the inventor conducted in-depth research on the above-mentioned problem, and then produced this case.

Contents of the invention

The purpose of the present invention is to provide a photoelectrochemical electrolysis equipment, which can integrate photochemical oxidation technology, photocatalytic oxidation technology and electrocatalytic oxidation technology, and make them form a synergistic effect, with fast degradation speed, high efficiency and simple structure advantage.

Another object of the present invention is to provide an electrode plate for the photoelectrochemical electrolysis equipment, which can realize the integration of photochemical oxidation technology, photocatalytic oxidation technology and electrocatalytic oxidation technology when used in conjunction with ultraviolet lamps, and make it A synergistic effect is formed, and the degradation speed of sewage is fast and the efficiency is high.

In order to achieve the above object, the solution of the present invention is:

Photoelectrochemical electrolysis equipment, including an electrolytic cell and a quartz tube arranged in the electrolytic cell, an ultraviolet lamp and an electrode plate, the ultraviolet lamp is erected in the quartz tube, and the electrolytic cell is provided with a sewage inlet and a treated water outlet; There are several sheets, and each electrode plate is placed flat and arranged at intervals from top to bottom. Each electrode plate has an anode part and a cathode part set in half, and the surface of the first half of the above electrode plate is coated with a Catalytically active metal oxide coating, the first half of the electrode plate is the above-mentioned anode part, the surface of the second half of the above-mentioned electrode plate is coated with a semiconductor photocatalyst coating with photocatalytic activity, the surface of the above-mentioned electrode plate The second half is the above-mentioned cathode part; among the two electrode plates arranged up and down, the anode part of the upper electrode plate and the cathode part of the lower electrode plate are vertically opposite to each other, and an insulating spacer is arranged between the two electrode plates. And the electrode plates are connected in series through insulating support rods, the above-mentioned quartz tubes stand upright through each of the above-mentioned electrode plates, and are tightly fitted with the above-mentioned electrode plates, and the upper ends of the above-mentioned quartz tubes go out of the above-mentioned electrolytic cell upwards.

There are several above-mentioned quartz tubes, and several above-mentioned ultraviolet lamps are arranged correspondingly to the above-mentioned quartz tubes one by one. Each of the above-mentioned ultraviolet lamps is electrically connected to an external power supply through wires.

The above-mentioned electrode plate is a mesh plate.

The above-mentioned electrode plate is a metal titanium plate, the above-mentioned metal oxide coating is a composite metal oxide coating containing RuO2 or a multi-component _oxide coating containing _IrO2 , and the above-mentioned semiconductor photocatalyst coating is Cu2O, ZnO, _{SnO 2.} An oxide coating in TiO ₂ , or the semiconductor photocatalyst coating is a composite coating composed of two or more oxides in Cu ₂ O, ZnO, SnO ₂ , and TiO ₂ .

The above composite metal oxide coatings are RuO ₂ -TiO ₂ composite metal oxide coatings, RuO ₂ -TiO ₂ -SnO ₂ composite metal oxide coatings, RuO ₂ -SnO ₂ composite metal oxide coatings, RuO ₂ - One of Ta ₂ O ₅ composite oxide coatings; the above multi-component oxide coatings are IrO ₂ -TiO ₂ binary oxide coatings, IrO ₂ -TiO ₂ -SnO ₂ ternary oxide coatings, IrO ₂ - one of SnO ₂ binary oxide coating and IrO ₂ -Ta ₂ O ₂ binary oxide coating.

The above-mentioned electrolytic cell has a square structure, and the above-mentioned electrolytic cell has a hollow structure with open upper and lower ends. The upper end face of the above-mentioned electrolytic cell is locked with an upper sealing cover that seals the upper opening of the electrolytic cell. The outlet pipe connected to the hollow chamber, the upper end of the above-mentioned quartz tube tightly passes through the upper sealing cover; the lower end face of the above-mentioned electrolytic cell is locked with a lower sealing cover that seals the lower opening of the electrolytic cell, and the above-mentioned lower sealing cover has a The hollow chamber communicates with the water inlet pipe.

The above-mentioned upper sealing cover and the lower sealing cover are metal titanium cover plates, and the opposite surface of the above-mentioned upper sealing cover and the above-mentioned lower sealing cover is coated with a layer of metal oxide coating with electrocatalytic activity, and the above-mentioned upper sealing cover and the lower sealing cover The covers are respectively electrically connected to the positive and negative poles of the external DC power supply.

The above-mentioned quartz tube and the above-mentioned upper sealing cover are sealed by a sealing sleeve set outside the quartz tube, and the above-mentioned upper sealing cover is provided with an installation hole for the sealing sleeve to pass through, and the above-mentioned sealing sleeve is embedded in the above-mentioned installation hole, and The outer wall of the sealing sleeve is concavely provided with a mounting groove for the hole edge of the mounting hole to tightly extend inside.

The support spacer has a hollow cylindrical structure, and the outer walls of the upper and lower ends of the support spacer are respectively protruding outwards with support rings stacked on the upper and lower sides of the electrode plate.

An electrode plate for photoelectrochemical electrolysis equipment, comprising an electrode plate body, the electrode plate body has an anode part and a cathode part set in half, and the surface of the first half of the electrode plate body is coated with electrocatalytic activity The metal oxide coating, the first half of the electrode plate body is the anode part, the surface of the second half of the electrode plate body is coated with a semiconductor photocatalyst coating with photocatalytic activity, the electrode plate body The second half of the part is the above-mentioned cathode part.

The above-mentioned electrode plate body has a porous structure.

The above-mentioned electrode plate body is a mesh plate, and several circular perforations are arranged on the above-mentioned mesh plate.

The above-mentioned electrode plate body is a metal titanium plate, the above-mentioned metal oxide coating is a composite metal oxide coating containing RuO2 or a multi-component _oxide coating containing _IrO2 , and the above _- mentioned semiconductor photocatalyst coating is Cu2O, ZnO, An oxide coating of SnO ₂ and TiO ₂ , or, the semiconductor photocatalyst coating is a composite coating composed of two or more oxides of Cu ₂ O, ZnO, SnO ₂ and TiO ₂ .

The above composite metal oxide coatings are RuO ₂ -TiO ₂ composite metal oxide coatings, RuO ₂ -TiO ₂ -SnO ₂ composite metal oxide coatings, RuO ₂ -SnO ₂ composite metal oxide coatings, RuO ₂ - One of Ta ₂ O ₅ composite oxide coatings; the above multi-component oxide coatings are IrO ₂ -TiO ₂ binary oxide coatings, IrO ₂ -TiO ₂ -SnO ₂ ternary oxide coatings, IrO ₂ - one of SnO ₂ binary oxide coating and IrO ₂ -Ta ₂ O ₂ binary oxide coating.

After adopting above-mentioned technical scheme, the beneficial effect of photoelectrochemical electrolysis equipment of the present invention is as follows:

(1), because half of the electrode plate is the anode part, and the other half is the anode part, and the anode part of the upper electrode plate in the upper and lower two electrode plates is arranged opposite to the negative plate part of the lower electric plate, then the two cathode parts There is an anode part between them, and the quartz tube passes through each electrode plate. In this way, the area formed between the two electrode plates has a cathode electrolysis area, an anode electrolysis area and an ultraviolet light irradiation area, which can convert the anodic oxygen evolution side reaction into Effective reaction, at the same time overcome the shortcomings of electrocatalytic oxidation or photocatalytic oxidation single technology, and form complementary advantages, so that the synergistic effect of photochemical oxidation technology, photocatalytic oxidation technology and electrocatalytic oxidation technology is good, so that the whole sewage can be degraded The process is fast and efficient;

(2) The quartz tube runs through each electrode plate, so the front and back of each electrode plate can be irradiated by ultraviolet light, and the effect of photocatalytic oxidation is better;

(3) The distance between the electrode plates can be adjusted arbitrarily, that is, the distance between the upper and lower cathodes and anodes can be adjusted arbitrarily, so that the tank pressure of the electrolytic cell can be effectively reduced by reducing the distance between the two electrodes, and the energy consumption is small , energy saving; and the number of electrode plates can be effectively adjusted according to the actual situation to meet the needs of different sewage treatment occasions in the actual situation; strong adaptability;

(4) The electrode plate is endowed with an electrocatalytically active anode area and a photocatalytically active cathode area at the same time, so that electrons can be directly conducted through the electrode plate without being transmitted through external wires, which reduces the resistance of the electron transfer process, that is, the photogenerated "electron-air" The smoother the separation of "hole" pairs, the better the separation effect of photogenerated "electron-hole" pairs, and the stronger the ability to generate strong oxidizing hydroxyl radicals.

After adopting the above-mentioned technical scheme, the electrode plate used for photoelectrochemical electrolysis equipment of the present invention, since the anode area of electrocatalytic activity and the cathode area of photocatalytic activity are simultaneously provided on the electrode plate body, the electrode plate body is used in conjunction with the ultraviolet lamp At the same time, it can realize the integration of photochemical oxidation technology, photocatalytic oxidation technology and electrocatalytic oxidation technology, and make them form a synergistic effect, and the degradation process of sewage is fast and efficient; at the same time, electrons can be directly conducted through the electrode plate body, It does not need to be transmitted through external wires, which reduces the resistance of the electron transport process, that is, the separation of photogenerated "electron-hole" pairs is smoother, and the separation effect of photogenerated "electron-hole" pairs is better, generating strong oxidizing hydroxyl radicals. The base is stronger.

Description of drawings

Fig. 1 is the perspective view of photoelectrochemical electrolysis equipment;

Fig. 2 is the assembly schematic diagram of electrode plate and quartz tube;

Figure 3 is a perspective view of the assembly of the electrode plate and the quartz tube

Fig. 4 is the schematic diagram of the assembly of quartz tube and upper sealing cover;

Fig. 5 is a schematic diagram of an electrode plate.

detailed description

The electrode plate 4 for photoelectrochemical electrolysis equipment of the present invention, as shown in Figure 5, comprises electrode plate body, and this electrode plate body has anode portion 4a and cathode portion 4b that are arranged in half, and electrode plate 4 is metal titanium plate, The surface of the first half of the electrode plate 4 is coated with an electrocatalytically active metal oxide coating (not shown), this metal oxide coating is a composite metal oxide coating containing RuO ₂ , this The composite metal oxide coating is RuO ₂ -TiO ₂ composite metal oxide coating, RuO ₂ -TiO ₂ -SnO ₂ composite metal oxide coating, RuO ₂ -SnO ₂ composite metal oxide coating, RuO ₂ -Ta One of the ₂ O ₅ composite oxide coatings; the first half of the electrode plate can constitute the anode part 4a, and the surface of the second half of the electrode plate 4 is coated with photocatalytically active semiconductor light Catalyst coating (not shown in the figure), the semiconductor photocatalyst coating is an oxide coating in Cu ₂ O, ZnO, SnO ₂ , TiO ₂ , that is, the second half of the electrode plate can constitute the Cathode part 4b. In this embodiment, the semiconductor photocatalyst coating can also be a composite coating composed of two or more oxides in Cu ₂ O, ZnO, SnO ₂ , TiO ₂ ; the metal oxide coating can also be a composite coating containing IrO ₂ multi-element oxide coating, this multi-element oxide coating is IrO ₂ -TiO ₂ binary oxide coating, IrO ₂ -TiO ₂ -SnO ₂ ternary oxide coating, IrO ₂ -SnO ₂ binary One of oxide coating and IrO ₂ -Ta ₂ O ₂ binary oxide coating.

The electrode plate 4 of the present invention is endowed with an electrocatalytically active anode region and a photocatalytically active cathode region at the same time, and when the electrode plate is used in conjunction with an ultraviolet lamp tube for treating sewage, it can realize the combination of photochemical oxidation technology, photocatalytic oxidation Technology and electrocatalytic oxidation technology are integrated to form a synergistic effect, and the degradation process of sewage is fast and efficient; at the same time, when in use, electrons can be directly conducted through the body of the electrode plate without transmission through external wires, reducing The resistance of the electron transport process is improved, that is, the separation of photogenerated "electron-hole" pairs is smoother, and the better the separation effect of photogenerated "electron-hole" pairs, the stronger the ability to generate strong oxidizing hydroxyl radicals.

In the present invention, the electrode plate body is a porous structure, preferably a mesh plate, and the mesh of the electrode plate 4 can be used for sewage to pass through the electrode plate 4. In this way, on the one hand, the sewage can be effectively contacted with the electrode plate, Moreover, the higher the effective contact procedure between sewage and electrode plates, the higher the efficiency of sewage degradation; on the other hand, it can ensure the smooth circulation of sewage.

In the present invention, the mesh plate is provided with several circular perforations 41, and the circular perforations 41 can be used for the installation of ultraviolet lamps, so as to realize the serial connection and cooperation of ultraviolet lamps and electrode plates, and the ultraviolet lamps and electrodes The series connection of the plates can make both the front and back of the electrode plate 4 irradiated by ultraviolet light, and the effect of photocatalytic oxidation is better.

Photoelectrochemical electrolysis equipment of the present invention, as shown in Figure 1-4, comprises electrolyzer 1, quartz tube 2, ultraviolet lamp 3 and electrode plate 4, wherein:

The electrolytic cell 1 is provided with a sewage inlet and a treated water outlet. The preferred structure of the electrolytic cell 1 is: the electrolytic cell 1 is a square structure, and the electrolytic cell is a hollow structure with its upper and lower ends open. The upper end face locks and seals the upper sealing cover 5 of the upper opening of the electrolytic cell 1. The upper sealing cover 5 is detachably locked together with the electrolytic cell 1 through the cooperation of the bolt 51 and the nut 52, that is, the upper end of the electrolytic cell 1 is convex along the periphery. There is an upper mounting ring 11 overlapping with the outer periphery of the upper sealing cover 5, and the upper mounting ring 11 and the upper sealing cover 5 are locked together through the cooperation of the bolt 51 and the nut 52; the lower end surface of the electrolytic cell 1 The lock has a lower sealing cover 6 that seals the opening of the lower end of the electrolytic cell 1, and the lower sealing cover 6 is detachably locked together with the electrolytic cell 1 through the cooperation of the bolt 61 and the nut 62, that is, the lower end of the electrolytic cell 1 is convexly arranged on the periphery. The lower mounting ring 12 that overlaps and cooperates with the outer periphery of the lower sealing cover 6, the lower mounting ring 12 and the lower sealing cover 6 are locked together by the cooperation of the bolt 61 and the nut 62; on the upper surface of the upper sealing cover 5 A water outlet pipe 53 communicated with the hollow chamber of the electrolytic cell 1 is fixedly erected, and the outlet pipe 53 is the outlet of the treated water. The lower bottom surface of the lower sealing cover 6 is fixedly erected with a water inlet pipe communicated with the hollow chamber of the electrolytic cell 1 63, this water inlet pipe 63 is the sewage inlet.

This quartz tube 2 and ultraviolet lamp 3 are all provided with several, and each quartz tube 2 and each ultraviolet lamp 3 are arranged one by one, and ultraviolet lamp 3 is erected in this quartz tube 2, and what described electrode plate 4 adopts this embodiment The electrode plates used for photoelectrochemical electrolysis equipment described in the method are not repeated here. The electrode plates 4 are provided with several sheets, and each electrode plate 4 is placed flat and arranged at intervals from top to bottom, and, Among the two electrode plates 4 arranged up and down, the anode portion 4a of the upper electrode plate 4 and the cathode portion 4b of the lower electrode plate 4 are vertically opposite to each other, and the two anode portions 4a of the two electrode plates 4 are dislocated up and down. Correspondingly, the portion 4b is also arranged in an up-and-down dislocation.

An insulating spacer 7 is arranged between the two electrode plates 4, preferably: the insulating spacer 7 is a hollow cylindrical structure, the insulating spacer 7 is erected, and each electrode plate is separated by the insulating spacer 7, and the insulating spacer 7 The outer sidewalls of the upper and lower ends of the upper and lower ends protrude outward respectively and are provided with a closed ring support ring 71, which can facilitate the placement and installation of the electrode plates 4, and the electrode plates 4 are connected in series through the insulating support rods 8, that is, Insulation support rods 8 pass through each insulation spacer 7, and tightly fit with insulation support rods 8 and electrode plates 4. Electrode plates 4 are provided with perforations 42 for the insulation support rods 8 to fit tightly through. The tight cooperation with the electrode plates 4 can realize the fixed installation of each electrode plate 4 .

Each quartz tube 2 passes through each electrode plate 4, and the lower end of the quartz tube 2 abuts against the lower sealing cover 6, and the upper end of the quartz tube 2 tightly fits through the upper sealing cover 5, and the quartz tube 2 and the upper sealing cover 5 are sealed and matched through the sealing sleeve 21 embedded outside the quartz tube 2, specifically: the upper sealing cover 5 is provided with an installation hole for the sealing sleeve 21 to pass through, and the sealing sleeve 21 is embedded In this mounting hole, and the outer side wall of the sealing sleeve 2 is provided with a mounting groove for the hole edge of the mounting hole to extend into the inside tightly, and the quartz tube 2 and the upper With the sealing fit of the sealing cover 5, the ultraviolet lamp 3 is connected with a wire 100 protruding from the quartz tube 2, and the wire 100 of each ultraviolet lamp 3 is electrically connected with an external power supply.

Photoelectrochemical electrolysis equipment of the present invention, its operating mechanism is:

The titanium dioxide layer of the cathode portion 4b of the electrode plate 4 is excited by ultraviolet light to obtain photogenerated electrons e- and photogenerated holes h+, and the reaction equation is as follows,

After the anode part 4a of the electrode plate 4 is energized to precipitate oxygen, the oxygen floats up and must contact the cathode part 4b above the anode part 4a. Capture photogenerated electrons on the cathode surface to generate superoxide ions O ₂ ^- , the reaction equation is as follows,

O ₂ +e ^- → O ₂ ^- (2)

Superoxide ion O ₂ ^- further reacts with hydrogen ions to produce hydrogen peroxide, and the reaction equation is as follows,

O ₂ ^- +2H ⁺ →H ₂ O ₂ (3)

Hydrogen peroxide is irradiated by ultraviolet rays to generate hydroxyl radicals (.OH) with stronger oxidation performance. The reaction equation is as follows,

After the photogenerated electrons are captured by oxygen, the recombination of photogenerated "electron-hole" pairs is effectively inhibited. Photogenerated holes react with hydroxide ions to generate strong oxidizing hydroxyl radicals. The reaction equation is as follows,

OH ^- +h ⁺ =·OH(5)

The above equations (1), (5) are the photocatalytic process; equations (2) (3) are the synergistic process of photocatalysis and electrocatalysis; It can be seen from this that the electrolysis equipment of the present invention can realize the integration of photochemical oxidation technology, photocatalytic oxidation technology and electrocatalytic oxidation technology, and the synergistic effect between the three.

The photoelectrochemical electrolysis device of the present invention has the following beneficial effects:

(1) Photochemical oxidation technology, photocatalytic oxidation technology and electrocatalytic oxidation technology can be integrated, and the anodic side reaction of oxygen evolution can be converted into an effective reaction, overcoming the shortcomings of electrocatalytic oxidation or photocatalytic oxidation single technology, And form complementary advantages, so that the synergistic effect of photochemical oxidation technology, photocatalytic oxidation technology and electrocatalytic oxidation technology is good, so that the whole degradation process of sewage is rapid and efficient;

(2) The quartz tube 2 runs through each electrode plate 4, so that the front and back surfaces of each electrode plate 4 can be irradiated by ultraviolet light, and the effect of photocatalytic oxidation is better;

(3) The distance between each electrode plate 4 can be adjusted arbitrarily, that is, the distance between the upper and lower cathodes and anodes can be adjusted arbitrarily, so that the cell pressure of the electrolytic cell can be effectively reduced by reducing the distance between the two electrodes (due to the cathode , the smaller the distance between the anodes, the lower the ohm of the sewage between the cathode and the anode will be, then work at the same current density, the lower the tank pressure), the energy consumption is small, and energy saving; and can be effectively adjusted according to the actual situation The number of electrode plates to meet the needs of different sewage treatment occasions in the actual situation; strong adaptability;

(4) The electrode plate is endowed with an electrocatalytically active anode area and a photocatalytically active cathode area at the same time, so that electrons can be directly conducted through the electrode plate without being transmitted through external wires, which reduces the resistance of the electron transfer process, that is, the photogenerated "electron-air" The smoother the separation of "hole" pairs, the better the separation effect of photogenerated "electron-hole" pairs, and the stronger the ability to generate strong oxidizing hydroxyl radicals.

(5) It has the advantages of simple structure, easy maintenance, convenient disassembly and assembly, and low manufacturing cost.

In the present invention, the upper sealing cover 5 and the lower sealing cover 6 are metal titanium cover plates, and the opposite surface of the upper sealing cover 5 and the lower sealing cover 6 is coated with a layer of metal oxide coating with electrocatalytic activity, and the upper The sealing cover 5 and the lower sealing cover 6 correspond to the positive and negative electrodes of the external DC power supply respectively, so that the upper and lower sealing covers 6 and 6 are used as anodes regardless of the characteristics of titanium metal and the conductive properties of the metal oxide coating. Or cathode use all have conductivity, then, when connecting external DC power supply, if upper sealing cover 5 connects external DC power positive pole, then lower sealing cover 6 then connects negative pole; If upper sealing cover 5 connects the negative pole of external DC power supply, then The lower sealing cover 6 is connected to the positive pole; so that when the photoelectrochemical electrolysis device of the present invention is connected to an external DC power supply box, there will be no wiring errors, which overcomes the problem of mistakenly connecting positive and negative in the traditional technology.

The above-mentioned embodiments and drawings do not limit the form and style of the product of the present invention, and any appropriate changes or modifications made by those skilled in the art should be considered as not departing from the patent scope of the present invention.

Claims (14)

1. a photoelectrochemistry electrolyzer, comprise electrolyzer and be located at silica tube, ultraviolet lamp and the battery lead plate in electrolyzer, this ultraviolet lamp is erected in this silica tube, this electrolyzer is provided with wastewater inlet and process water out; It is characterized in that: above-mentioned battery lead plate is provided with some, each battery lead plate keeps flat setting, and in being from top to bottom spaced, each battery lead plate has anode portion and the negative pole part of double setting, the first half portion faces of above-mentioned battery lead plate are coated with the coating of metal oxides with electro catalytic activity, the first half positions of this battery lead plate are above-mentioned anode portion, the surface-coated at the second half positions of above-mentioned battery lead plate has the semiconductor light-catalyst coating with photocatalytic activity, and the second half positions of above-mentioned battery lead plate are above-mentioned negative pole part;

The anode portion being in the battery lead plate of top in two battery lead plates setting up and down is be oppositely arranged up and down with the negative pole part of the battery lead plate being in below, insulating spacer is provided with between two battery lead plates, and each battery lead plate is serially connected by insulating support rod, above-mentioned silica tube is erect through each above-mentioned battery lead plate, and overlap wringing fit with above-mentioned battery lead plate, and the end, upper end of above-mentioned silica tube upwards passes outside above-mentioned electrolyzer.

2. photoelectrochemistry electrolyzer as claimed in claim 1, it is characterized in that: above-mentioned silica tube is provided with several, above-mentioned ultraviolet lamp is correspondingly provided with several, and with the corresponding setting one by one of above-mentioned silica tube, each above-mentioned ultraviolet lamp is connected with extraneous power electric by wire.

3. photoelectrochemistry electrolyzer as claimed in claim 1, is characterized in that: above-mentioned battery lead plate is mesh plate.

4. photoelectrochemistry electrolyzer as claimed in claim 1, is characterized in that: above-mentioned battery lead plate is metallic titanium plate, and above-mentioned coating of metal oxides is for containing RuO ₂complex metal oxides coating or containing IrO ₂multinary oxide coating layer, above-mentioned semiconductor light-catalyst coating is Cu ₂o, ZnO, SnO ₂, TiO ₂in a kind of oxide coating, or above-mentioned semiconductor light-catalyst coating is Cu ₂o, ZnO, SnO ₂, TiO ₂in two or more oxide compound composition compound coating.

5. photoelectrochemistry electrolyzer as claimed in claim 4, is characterized in that: above-mentioned complex metal oxides coating is RuO ₂-TiO ₂complex metal oxides coating, RuO ₂-TiO ₂-SnO ₂complex metal oxides coating, RuO ₂-SnO ₂complex metal oxides coating, RuO ₂-Ta ₂o ₅one in composite oxide coating; Above-mentioned multinary oxide coating layer is IrO ₂-TiO ₂binary oxide coating, IrO ₂-TiO ₂-SnO ₂ternary oxide coating, IrO ₂-SnO ₂binary oxide coating, IrO ₂-Ta ₂o ₂one in binary oxide coating.

6. photoelectrochemistry electrolyzer as claimed in claim 1, it is characterized in that: above-mentioned electrolyzer is square structure, above-mentioned electrolyzer is its upper and lower two ends is the hollow structure of open state, the upper end end face locking of above-mentioned electrolyzer has the top cover labyrinth of sealed electrolytic cell upper end open, above-mentioned top cover labyrinth has the rising pipe communicated with the hollow chamber of electrolyzer, the end, upper end of above-mentioned silica tube closely passes outside top cover labyrinth; The lower end surface locking of above-mentioned electrolyzer has the lower sealing cover of sealed electrolytic cell lower ending opening, above-mentioned lower sealing cover has the water inlet pipe communicated with the hollow chamber of electrolyzer.

7. photoelectrochemistry electrolyzer as claimed in claim 6, it is characterized in that: above-mentioned top cover labyrinth and lower sealing cover are metal titanium cover plate, the opposite face that above-mentioned top cover labyrinth is relative with above-mentioned lower sealing cover is coated with the coating of metal oxides that one deck has electro catalytic activity, and above-mentioned top cover labyrinth and lower sealing cover are corresponding to be respectively electrically connected with the positive and negative electrode of external dc power.

8. photoelectrochemistry electrolyzer as claimed in claim 6, it is characterized in that: sealed by the seal cartridge be sleeved on outside silica tube between above-mentioned silica tube and above-mentioned top cover labyrinth, above-mentioned top cover labyrinth offers the open holes passed for seal cartridge, above-mentioned seal cartridge is flush-mounted in above-mentioned open holes, and the edge, hole that the outer side wall of seal cartridge is arranged with for open holes is closely inserted into interior installation groove.

9. photoelectrochemistry electrolyzer as claimed in claim 1, it is characterized in that: above-mentioned support distance piece is hollow columnar structures, respectively to being convexly equipped with the support ring being stacked at battery lead plate upper and lower surface outward on the upper/lower terminal end outer side wall of above-mentioned support distance piece.

10. the battery lead plate for photoelectrochemistry electrolyzer, comprise plate electrode body, it is characterized in that: above-mentioned plate electrode body has anode portion and the negative pole part of double setting, the first half portion faces of above-mentioned plate electrode body are coated with the coating of metal oxides with electro catalytic activity, the first half positions of this plate electrode body are above-mentioned anode portion, the surface-coated at the second half positions of above-mentioned plate electrode body has the semiconductor light-catalyst coating with photocatalytic activity, and the second half positions of above-mentioned plate electrode body are above-mentioned negative pole part.

11. battery lead plates for photoelectrochemistry electrolyzer according to claim 10, is characterized in that: above-mentioned plate electrode body is vesicular structure.

12. battery lead plates for photoelectrochemistry electrolyzer according to claim 11, is characterized in that: above-mentioned plate electrode body is mesh plate, above-mentioned mesh plate is provided with several circular perforations.

13. battery lead plates for photoelectrochemistry electrolyzer according to claim 10, is characterized in that: above-mentioned plate electrode body is metallic titanium plate, and above-mentioned coating of metal oxides is for containing RuO ₂complex metal oxides coating or containing IrO ₂multinary oxide coating layer, above-mentioned semiconductor light-catalyst coating is Cu ₂o, ZnO, SnO ₂, TiO ₂in a kind of oxide coating, or above-mentioned semiconductor light-catalyst coating is Cu ₂o, ZnO, SnO ₂, TiO ₂in two or more oxide compound composition compound coating.

14. battery lead plates for photoelectrochemistry electrolyzer according to claim 13, is characterized in that: above-mentioned complex metal oxides coating is RuO ₂-TiO ₂complex metal oxides coating, RuO ₂-TiO ₂-SnO ₂complex metal oxides coating, RuO ₂-SnO ₂complex metal oxides coating, RuO ₂-Ta ₂o ₅one in composite oxide coating; Above-mentioned multinary oxide coating layer is IrO ₂-TiO ₂binary oxide coating, IrO ₂-TiO ₂-SnO ₂ternary oxide coating, IrO ₂-SnO ₂binary oxide coating, IrO ₂-Ta ₂o ₂one in binary oxide coating.