CN101693560B - Integral solar energy photoelectricity water-treatment device - Google Patents

Abstract

The invention relates to an integrated solar photoelectric water treatment device. It includes electrode pairs or three-dimensional electrodes loaded with photocatalytic materials and electrolytic cells, battery packs, solar cell components and corresponding controllers, ultraviolet lamps; ultraviolet lamps are used to illuminate photoelectrodes; solar cell components convert received solar light energy For post-transmission and storage of electrical energy in battery packs, intermittently or continuously supply power to UV lamps and/or electrode pairs. The invention integrates photochemical oxidation and electrochemical oxidation process, the two produce enhanced and synergistic effects, can improve water treatment efficiency, and can also play the role of photochemical oxidation or electrochemical oxidation process alone to realize water purification, with simple structure and low manufacturing cost , safe and simple to operate, easy to realize automation and safe maintenance, can fully or partially use the electric energy converted from solar energy to drive the entire water treatment process, solve the problem that the photoelectric catalytic water treatment process is highly dependent on energy, and can operate without relying on existing power grid.

Description

Integrated solar photoelectric water treatment device

technical field

The invention relates to the field of sewage treatment, in particular to an integrated solar photoelectric water treatment device.

Background technique

With the development and improvement of wastewater treatment technology, organic wastewater with simple components and good biodegradability has been effectively controlled. Biological method is currently the most economical and effective method to eliminate organic pollutants in domestic and industrial wastewater. However, with the rapid development of petrochemical, pharmaceutical, pesticide and fuel industries, the number and types of refractory organic compounds in industrial wastewater are increasing day by day, especially containing high concentrations of aromatic compounds, such as phenolic (three) substances, etc. It is highly toxic and difficult to remove directly by general biodegradation methods. On the other hand, the country's limit standards for pollutant discharge are getting higher and higher, so it is urgent to study new methods and technologies for wastewater treatment.

In recent years, some oxidation technologies have been developed, such as chemical oxidation, photochemical oxidation, catalytic oxidation, electrochemical oxidation, etc. Water treatment electrochemical oxidation technology and photoelectric catalytic oxidation technology belong to advanced oxidation process (Advanced Oxidation Processes, AOPs), which can produce strong oxidants such as hydroxyl radicals, hydrogen peroxide and ozone, which can not only sterilize and disinfect, but also realize the removal of organic pollutants. Rapid degradation and even complete mineralization. Advanced oxidation technologies, especially electrochemical and photocatalytic oxidation technologies, are different from biological treatment methods. They are easy to automate and easy to operate. They are typical water treatment and water purification technologies with direct application prospects. Due to the effective treatment of refractory organic wastewater, simple operation, easy automation, and good environmental compatibility, electrochemical oxidation technology is an important development direction of electrochemical wastewater treatment technology. However, for the electrochemical oxidation process, the accumulation of quinones is easy to occur during the degradation of organic pollutants, and the ring-opening reaction of quinones and aromatic substances is the slowest reaction step in a series of reactions. The substance may be more toxic than the original organic pollutant. From this point of view, it is imperative to improve the oxidation efficiency of the electrochemical oxidation process to quickly remove quinones. In addition, the energy that supports the electrochemical oxidation process and the generation of ultraviolet radiation generally comes from the electrical energy delivered by the grid, which limits the application of electrochemical oxidation technology and photocatalytic oxidation technology.

Contents of the invention

The technical problem to be solved by the present invention is to provide a photoelectric integrated water treatment device driven by solar energy, which can fully or partially use the electric energy converted from solar energy to drive the electrochemical oxidation process, photoelectric catalytic oxidation process and ultraviolet radiation system, thereby Realize the fully automatic sterilization and disinfection of polluted raw water or waste water and the degradation and removal of organic and inorganic pollutants.

In order to solve the above technical problems, the present invention adopts the following technical solutions,

An integrated solar photoelectric water treatment device includes:

At least one set of solar cell components and corresponding current controllers;

at least one battery pack;

at least one set of corresponding photoelectrodes (anodes) and counter electrodes (cathodes), or at least one set of three-dimensional electrodes;

at least one UV lamp;

at least one electrolyzer;

The photoelectrode and the counter electrode are correspondingly arranged in the electrolytic cell, the electrolytic cell is provided with a water inlet and a water outlet, the photoelectrode is an ultraviolet light or/and visible light catalytically active photoelectrode; the ultraviolet lamp is used to illuminate the photoelectrode ; The solar cell assembly converts the received solar energy into electrical energy and then transmits and stores it in the storage battery pack, which supplies power to the ultraviolet lamp and/or electrode pair intermittently or continuously.

In the device of the present invention, the combination of photocatalysis and electrochemistry is mainly to load the semiconductor photocatalyst on the conductive substrate by immobilization technology to make a photoelectrode, and the solar cell assembly generates electric energy, and through the controller (the role of the controller is to control The working status of the entire system, and protect the battery from overcharge and overdischarge; in places with large temperature differences, qualified controllers should also have the function of temperature compensation; other additional functions such as light control switches, time control The switch should be an option of the controller;) and the battery pack to adjust the power distribution during the day and night, drive the electrode to undergo electrochemical oxidation process and apply ultraviolet radiation on the electrode surface as large as possible to generate photoelectric catalytic oxidation process, and at the same time The highly oxidizing HO free radicals produced by photoelectrocatalysis can rapidly degrade organic pollutants and kill bacteria and viruses.

Anode materials suitable for electrochemical oxidation treatment of refractory organics generally need to meet the conditions of good conductivity, low power loss, good stability, acid and alkali corrosion resistance, ability to withstand a certain temperature, good adsorption performance, and high electrocatalytic activity. .

The photoelectrode is DSA, PbO ₂ , SnO ₂ , Sb ₂ O ₃ , RuO ₂ , WO ₃ , TiO ₂ , IrO ₂ , Bi ₂ O ₃ electrodes loaded with photocatalytic materials, or a composite electrode of the above metal oxides .

Loading photocatalytic materials on electrodes (electrode modification) can be carried out by chemical and physical chemical methods. Create a certain microstructure on the surface of the electrode, endow the electrode with a predetermined function, and selectively perform the desired reaction on the electrode, thereby realizing the functional design of the electrode. This process can greatly reduce the catalyst consumption and improve the catalytic efficiency. The method of modifying the electrode can be divided into the following types: electroplating, electroless plating or composite plating method, thermal decomposition method, ion implantation, spraying and other physical methods. Electroplating is to deposit the modifier on the surface of the electrode under the action of direct current. By controlling the appropriate electroplating conditions, such as pH value, current density, temperature and the formulation of the electroplating solution, a metal alloy coating with higher catalytic activity than the base electrode can be obtained. Electroless plating is to use a reducing agent to reduce and deposit metal ions in the plating solution on the electrode surface to form a metal coating without the passage of external current; electroless plating requires complex electrolytic equipment, and has uniform coating, good corrosion resistance, etc. Advantages, composite plating is to deposit a small amount of solid particles insoluble in the plating solution and the metal to be plated on the modified electrode to form a composite coating with special functions; the thermal decomposition method is to coat the surface of the modified electrode with a certain concentration of metal salt solution, and then heated under specific conditions to decompose the metal salt solution into metal oxides or metal sulfides, which adhere to the surface of the electrode and modify the electrode as a catalytic active substance; modifying the electrode with physical methods has its unique advantages , such as the thickness of the modified layer is uniform, the binding force with the carrier is good, and it is usually not limited by the type of the modified substance.

The solar photoelectric water treatment device is provided with an external power supply interface for supplying power to the electrode pair and/or ultraviolet lamp; when the energy of the solar battery is insufficient, it can be converted to line power supply to realize photoelectric complementarity and ensure the electrolytic cell under any weather conditions normal work.

The photoelectrodes are in any one of mesh shape, sheet shape, block shape, line shape and cylinder shape.

In order to increase the specific surface area of the electrode, the electrode can be made into a variety of shapes such as porous, mesh, spherical, ring, etc., and a three-dimensional electrode reactor can also be used. The three-dimensional electrode is filled with granular or other broken pieces between the traditional two-dimensional electrodes. The chip-like working electrode material is formed by charging the surface of the filled electrode material. The three-dimensional electrode has a large specific surface area and can provide a large current intensity at a low current density. It can be used to treat heavy metal ion wastewater .

The counter electrode and the photoelectrode are arranged in parallel or coaxially, and the distance between the two is 10-200 mm. The counter electrode is made of any one of stainless steel, carbon fiber, graphite, nickel, titanium, iron, and aluminum .

The working voltage of the electrode pair is 0<~20V, and the current density is 0<~30mA/cm ² .

The position of the ultraviolet lamp is such that the emitted ultraviolet light is vertically irradiated on the photoelectrode, so that the photoelectrode can obtain the maximum illuminance.

The electrolytic cell is in the shape of a cuboid or a cylinder.

When the integrated solar photoelectric water treatment device is in operation, the raw water or waste water to be treated is input into the electrolytic cell in an intermittent or continuous and cyclic manner, and a conductive medium can be added to the waste water or raw water to enhance the conductivity of the solution when necessary. It can realize the automatic operation of raw water or wastewater treatment. The depth of the water flow is generally controlled within 50cm, and the width of the water flow is within the range that the ultraviolet light emitted by the ultraviolet lamp can irradiate. The projection shape of the electrolytic cell should adopt a square design. The light is designed as a coaxial cylinder.

The electrolytic cell is open, so that the photoelectrode can receive sunlight.

Sunlight is an inexhaustible and inexhaustible energy source. There are 4 to 6% of the light energy in sunlight to stimulate the catalyst. For the open-air reaction tank system, the sunlight can be directly irradiated on the reaction tank, and its ultraviolet light can It is directly utilized as a photocatalytic light source. At the same time, the solar photovoltaic cell system in the system converts solar energy into electric energy to supply power for the ultraviolet lamp installed in the electrolytic cell to form a second photocatalytic light source.

The present invention has positive and beneficial effects:

1. The device integrates the process of photochemical oxidation and electrochemical oxidation, which can not only produce strengthening and synergistic effects, improve water treatment efficiency, but also can achieve water purification through the role of photochemical oxidation or electrochemical oxidation process alone. The inventor used the commercialized DSA electrode as the photoelectrode and carried out photocatalytic degradation with 1,4-benzoquinone as the model pollutant. The results showed that the removal rate of TOC in the photocatalytic oxidation process was the highest among the single photocatalytic oxidation and electrocatalytic oxidation processes. and 1.25 times of that, the photocatalytic degradation process has a higher degradation efficiency, which proves that the coupling of photocatalytic oxidation and electrocatalytic oxidation produces a certain synergistic effect; the photocatalytic oxidation process dominated by electrochemical oxidation can be highly efficient Hydroxyl radicals can be generated, and the degradation efficiency can be adjusted, which is of great practical value in water treatment.

2. The structure is simple, the manufacturing cost is low, the operation is safe and simple, and it is easy to realize automation and safe maintenance. It can fully or partially use the electric energy converted from solar energy to drive the entire water treatment process, which solves the problem that the photoelectric catalytic water treatment process is highly dependent on energy. , the operation can not rely on the existing power grid.

3. The device of the present invention has high energy efficiency and mild reaction conditions, and can generally be carried out at normal temperature and pressure.

4. It is suitable for the follow-up advanced treatment of toxic and biodegradable pollutants and sewage.

5. Using clean energy and solar energy, it can treat a variety of organic and inorganic pollutants at the same time, and achieve the effect of sterilization and disinfection. It is a green and environmentally friendly water treatment technology and device. If all or part of the solar energy is used to drive the electrochemical oxidation process, photocatalytic oxidation process and ultraviolet radiation, then water purification and sterilization will become free from geographical and time constraints, not only easy to be fully automated, but also more efficient. Convenient and economical.

Description of drawings

Figure 1 is an integrated solar photoelectric water treatment device.

Detailed ways

Embodiment 1 Integrated solar photoelectric water treatment device, referring to Fig. 1, comprises a group of solar cell assemblies (8W) 2 and corresponding controller 3 (power supply Co., Ltd), a group of battery packs 4, a group of corresponding Photoelectrode 5 and counter electrode 6, an ultraviolet lamp 7, a rectangular parallelepiped electrolytic cell 9; Photoelectrode 5 and counter electrode 6 are correspondingly arranged in electrolytic cell 9, and photoelectrode 5 is positioned at the top of counter electrode 6, both Spacing 20cm, the electrolytic cell 9 is provided with a water inlet 10 and a water outlet 11, and the photoelectrode is an ultraviolet light or/and visible light catalytically active photoelectrode; the ultraviolet lamp 7 is used to illuminate the photoelectrode 5, to the photoelectrode 5 and Raw water or waste water 8 provides ultraviolet radiation; the solar cell assembly 2 converts the received solar light energy 1 into electrical energy and then transports and stores it in the battery pack 4, which supplies power to the ultraviolet lamp and/or electrode pair intermittently or continuously .

Utilize above-mentioned treatment device to directly electrochemically oxidize acid orange II (azo dye) simulated waste water under indoor weak light condition, use commercialized solar cell module 2, photoelectrode 5 is DSA electrode, with titanium mesh as counter electrode 6, The ultraviolet lamp 7 is not turned on, the initial concentration is 10mg/L, the concentration of sodium chloride is 0.1mol/L, and the pH is 6.8. The chromaticity removal rate reaches 2.1%, 10.9% and 24.7% when the reaction time is 5min, 30min and 60min respectively .

Embodiment 2 Utilizes the integrated solar photoelectric water treatment device described in Embodiment 1 to directly Electrochemical oxidation treatment of acid orange II (azo dye) simulated wastewater, using commercial solar cell modules (8W), using commercial DSA electrodes as working electrodes, using titanium mesh as counter electrodes, initial concentration 10mg/L, sodium chloride The concentration is 0.1mol/L, the pH is 6.8, and the color removal rate has reached 100% when the reaction time is 5 minutes.

Embodiment 3 The integrated solar photoelectric water treatment device is basically the same as Embodiment 1, and the device is used to directly electrochemically oxidize the acidic acid under the conditions of outdoor sunlight (from 11:00 to 13:00 on September 15, 2009, Zhengzhou). Orange II (azo dye) simulated wastewater uses a commercial solar cell module (8W), with a commercial DSA electrode as the working electrode and a titanium mesh as the counter electrode, with an initial concentration of 10mg/L, without adding electrolytes such as sodium chloride, pH 6.8, the chroma removal rate reached 22.1%, 74.1% and 91.8% when the reaction time was 5min, 30min and 60min, respectively.

Embodiment 4 The integrated solar photoelectric water treatment device is basically the same as Embodiment 1, and the device is used to directly electrochemically oxidize the acidic acid under the conditions of outdoor sunlight (from 11:00 to 13:00 on September 15, 2009, Zhengzhou). Orange II (azo dye) simulated wastewater, using commercial solar cell modules (8W), using commercial DSA electrodes as working electrodes, using titanium mesh as counter electrodes, turning on the UV lamp, initial concentration 10mg/L, no chlorination was added Sodium and other electrolytes, pH6.8, the color removal rate has reached 100% when the reaction time is 5 minutes.

Example 5 The integrated solar photoelectric water treatment device is basically the same as that of Example 1. This device is used to take raw drinking water and add bacteria-containing water to make the raw water to be treated. The total number of bacteria before treatment is 6×10 ⁷ /mL. The conditions of embodiment 4 were processed, and the treatment time was 60min, and the total number of bacteria became 0.

Embodiment 6 The integrated solar photoelectric water treatment device is basically the same as Embodiment 1, except that the photoelectric electrode used is a TiO ₂ electrode, and the electrode is made of carbon fiber.

Embodiment 7 The integrated solar photoelectric water treatment device is basically the same as Embodiment 1, the difference lies in: filling granular or other detritus-like working electrode materials between the two electrodes to form a three-dimensional electrode.

Embodiment 8 The integrated solar photoelectric water treatment device is basically the same as Embodiment 1, except that two sets of solar battery groups are provided; two electrolytic cells are connected in series, each electrolytic cell is provided with a corresponding electrode and UV lamps.

Embodiment 9 The integrated solar photoelectric water treatment device is basically the same as Embodiment 1, except that the electrolytic cell and electrodes are coaxial cylindrical, the photoelectrode is on the outside, and the counter electrode is on the inside.

Claims (6)

1. integral solar energy photoelectricity water-treatment device is characterized in that it comprises:

At least one group of solar module and corresponding controller;

At least one group storage battery group;

At least one group of corresponding optoelectronic pole and counter electrode, or at least one group of three-diemsnional electrode;

At least one ultra-violet lamp;

The rectangular-shaped electrolyzer of at least one opened type;

Said optoelectronic pole and counter electrode are arranged in the electrolyzer accordingly, and this electrolyzer is provided with water-in and water outlet, and the flow depth in this electrolyzer generally is controlled in the 50cm, and flow width is the scope that UV-light that uv lamp sends can shine; Said photoelectricity very load has DSA, the PbO of photocatalyst material ₂, SnO ₂, Sb ₂O ₃, RuO ₂, WO ₃, IrO ₂, Bi ₂O ₃Electrode, or be the combined electrode of above-mentioned MOX; Said uv lamp is used for the irradiates light electrode, and its present position can make its UV-light vertical irradiation that sends on optoelectronic pole; Secondary battery is carried, is stored in to said solar module after the solar energy that receives is converted into electric energy, and this secondary battery intermittently or be that uv lamp and/or electrode pair are supplied power continuously.

2. according to the said integral solar energy photoelectricity water-treatment device of claim 1, it is characterized in that said photoelectricity is very netted, in the sheet, bulk, wire, tubular any one.

3. according to the said integral solar energy photoelectricity water-treatment device of claim 2, it is characterized in that, in said solar energy photoelectricity water-treatment device, be provided with external power interface to electrode pair and/or uv lamp power supply.

4. according to any said integral solar energy photoelectricity water-treatment device of claim of claim 1～3; It is characterized in that; Said counter electrode is corresponding with optoelectronic pole to laterally arrange or the concentric setting; Between the two apart from being 10～200mm, said counter electrode is processed by in stainless steel, thomel, graphite, nickel, titanium, iron, the aluminium any one.

5. according to the said integral solar energy photoelectricity water-treatment device of claim 4, it is characterized in that, the WV of said electrode pair is 0＜～20V, current density is 0＜～30mA/cm ²

6. according to the said integral solar energy photoelectricity water-treatment device of claim 5; It is characterized in that; When said integral solar energy photoelectricity water-treatment device moves; With the former water that is processed or waste water with intermittently or continuously, the round-robin mode imports in the electrolyzer, can in being processed waste water or former water, add conducting medium when needing, and strengthens the electroconductibility of solution.

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