CN106006860A - High-salinity organic wastewater treatment device powered by solar energy - Google Patents
High-salinity organic wastewater treatment device powered by solar energy Download PDFInfo
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- 239000007800 oxidant agent Substances 0.000 claims description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 3
- 239000007784 solid electrolyte Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000004966 Carbon aerogel Substances 0.000 claims description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
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- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910006694 SnO2—Sb2O3 Inorganic materials 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
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- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 2
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- 239000013618 particulate matter Substances 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 6
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4691—Capacitive deionisation
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S10/00—PV power plants; Combinations of PV energy systems with other systems for the generation of electric power
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/138—Water desalination using renewable energy
- Y02A20/142—Solar thermal; Photovoltaics
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/208—Off-grid powered water treatment
- Y02A20/212—Solar-powered wastewater sewage treatment, e.g. spray evaporation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention provides a high-salinity organic wastewater treatment device powered by solar energy. The device is characterized by comprising at least one electrochemical oxidation electrolysis tank 105, a capacitor deionizing desalting device 110 and a solar power supply device 103, wherein each electrolysis tank 105 comprises an electrochemical anode 202, an electrochemical cathode 206 and a tank body, the capacitor deionizing desalting device 110 comprises at least a group of capacitor deionizing units 301, and the solar power supply device 103 is used for powering the electrolysis tanks 105 and the capacitor deionizing desalting device 110 and serves as a direct-current power source of the electrolysis tanks and the capacitor deionizing desalting device. The invention further provides a high-salinity organic wastewater treatment method based on the high-salinity organic wastewater treatment device.
Description
Technical Field
The invention relates to a solar-powered high-salinity organic wastewater treatment device, and belongs to a water treatment technology in the field of environmental protection.
Background
The refractory organic waste water containing high salt content, such as waste water from coking, tanning, paper making, chemical industry, food and chlor-alkali industry and garbage percolate, contains a great amount of toxic refractory organic pollutants and inorganic salts, such as Cl-,SO4 2-,Na+,Ca2+If the plasma is not treated or only organic matters are removed, the high-salinity organic matter wastewater inevitably has great influence on the water quality of water body organisms and industrial and agricultural production water. The seeking of economic and efficient high-salinity organic wastewater treatment technology is extremely important when water resources are increasingly short and the discharge amount of saline wastewater is increasingly increased.
The traditional biochemical treatment technology is used for obtaining satisfactory treatment effect on the high-salt-content degradation-resistant organic wastewater. The high salinity organic wastewater has good conductivity, so that the electrochemical treatment is a proper choice. The organic pollutants in the water can be effectively degraded by oxidation by utilizing free radicals (such as hydroxyl free radicals) generated in the electrochemical oxidation process or generated oxidizing agents (such as hypochlorous acid). In addition, wastewater desalination is an essential link for recycling high-salinity wastewater, salt content is one of main limiting indexes for recycling industrial wastewater, and only removing organic matters cannot meet the recycling and discharge standards of the high-salinity organic wastewater. The high energy consumption of multi-effect evaporation and desalination technologies based on membrane permeation technologies limits their wide application. The recently developed Capacitive Deionization (CDI) desalination is a novel water treatment desalination technology, and has the advantages of high desalination rate, low energy consumption, no need of chemical regeneration, strong pollution resistance and the like. The working principle of the capacitive deionization technology is established on the theory of double electric layers, under the action of an electric field, cations in the solution are adsorbed on the surface of a negative electrode, meanwhile, anions are adsorbed on the surface of a positive electrode, and the ion concentration of the solution is gradually reduced along with continuous adsorption of ions, so that the solution desalination is realized.
However, the main problem of the electrochemical technology is that a large amount of electric energy is consumed, which becomes a key factor for restricting the development of the related technology. In addition, the treatment of the high-salinity refractory organic wastewater is often required to be carried out in the field, and the field is often not provided with power supply conditions. Further, the compactness and portability of the device are also urgent practical requirements.
Disclosure of Invention
According to one aspect of the present invention, there is provided a solar-powered high-salinity organic wastewater treatment apparatus, characterized by comprising:
at least one electrochemical oxidation electrolytic cell is provided,
a capacitance deionization desalination device, a device,
a solar energy power supply device is arranged on the solar energy power supply device,
wherein,
each electrolytic cell comprises an electrochemical anode, an electrochemical cathode and a cell body,
the capacitive deionization and desalination device comprises at least one group of capacitive deionization units,
the solar power supply device is used for supplying direct current power to the electrolytic cell and the capacitance deionization and desalination device and is used as a direct current power supply of the electrolytic cell and the capacitance deionization and desalination device.
According to a further aspect of the present invention, there is provided a method for treating high-salinity organic wastewater, characterized by comprising:
A) the wastewater to be treated continuously enters the anode chamber and the cathode chamber of the electrolytic cell through the anode water inlet and the cathode water inlet respectively,
B) electrolyzing the wastewater to be treated in the anode chamber and the cathode chamber in a constant current charging mode under the action of external direct current (2-4V) applied by an anode current collector and a cathode current collector,
C) the wastewater in the anode chamber and the cathode chamber respectively flows out of the electrolytic cell through the anode water outlet and the cathode water outlet and enters the capacitive deionization desalination device,
D) leading the effluent from the electrochemical oxidation electrolytic tank to enter a desalting chamber in the third gasket through a water inlet on the hollow third gasket, leading the water treated in the desalting chamber out of a water outlet on the third gasket to be used as the effluent of the capacitive deionization desalting device,
E) applying 1.0-1.5V direct current to the first electrode of the carbon-based capacitor and the second electrode of the carbon-based capacitor to perform capacitive adsorption deionization, outputting the effluent of the capacitive deionization desalination device as desalted water,
F) when the conductivity of the effluent of the capacitive deionization and desalination device is continuously increased from low to close to the conductivity of the influent, the power supply to the capacitive deionization and desalination device is stopped, the two electrodes of the first electrode of the carbon-based capacitor and the second electrode of the carbon-based capacitor of the capacitive deionization and desalination device are in short circuit and/or are in reverse direct current connection, the capacitor is released to adsorb ions, and the effluent of the capacitive deionization and desalination device is output as strong brine,
G) when the conductivity of the effluent of the capacitive deionization desalting device is continuously reduced from high to the conductivity of the influent, the direct current of 1.0-1.5V is switched on again for desalting,
H) repeating the above steps E) to G).
Drawings
FIG. 1 is a diagram of a solar powered electrochemical oxidation-capacitive deionization desalination coupling apparatus according to one embodiment of the present invention.
FIG. 2 is a schematic view of a "zero pole pitch" solid electrolyte cell arrangement according to one embodiment of the present invention.
FIG. 3 is a schematic diagram of a capacitive deionization apparatus according to one embodiment of the present invention.
Detailed Description
In view of the problems in the prior art, the inventor of the present invention has realized through intensive research that the solar power supply device is used to provide electric support for a Capacitive Deionization (CDI) desalination device, and the waste water electrooxidation technology is combined with the capacitive deionization desalination technology, that is, the electrochemical oxidation-capacitive deionization desalination coupling technology of solar power supply can simultaneously remove and desalinate organic matters in high-salt refractory organic waste water. The technical scheme of the invention can greatly reduce the treatment cost of the high-salt degradation-resistant organic wastewater, shorten the treatment time and reduce secondary pollution, is especially suitable for the field environment lacking power supply, and has substantial improvement on the aspects of compactness and portability of the device.
The invention aims to design a novel electrochemical treatment device for high-salt refractory organic wastewater with low energy consumption, and solves the problem of synchronous treatment of effective removal and desalination of refractory organic matters.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
as shown in fig. 1, a solar powered high salinity organic wastewater treatment apparatus according to one embodiment of the present invention includes a wastewater pretreatment apparatus, one or more electrochemical oxidation electrolysis cells 105, a capacitive deionization apparatus 110, and a solar powered apparatus 103. The solar power supply device 103 is used as a direct current power supply for the electrochemical oxidation electrolytic cell and the capacitive deionization desalination device, and the power output ends of the solar power supply device are connected to the electrochemical oxidation electrolytic cell 105 and the capacitive deionization desalination device 110 so as to provide the power required by the operation of the electrochemical oxidation electrolytic cell 105 and the capacitive deionization desalination device 110.
In one embodiment, the wastewater pretreatment device is a pretreatment water tank 101 for treating insoluble suspended particulate matter in water to prevent fouling of subsequent treatment devices; the inlet water 100 of the pretreatment device is wastewater to be treated, and the outlet water of the pretreatment device is communicated to an electrochemical oxidation electrolytic cell 105. In one embodiment, a first water pump 102 is disposed between the water collection tank 101 and the electrochemical oxidation electrolyzer 105, as shown in FIG. 1.
At least one electrochemical oxidation electrolytic cell 105 is arranged downstream of the wastewater pretreatment device; when two or more electrolytic cells 105 are provided, the electrolytic cells 105 are arranged in parallel with each other.
The electrolytic cell 105 may be an open electrolytic cell or a closed electrolytic cell.
According to one embodiment of the invention, each cell 105 includes an electrochemical anode 202, an electrochemical cathode 206, and a housing (not shown).
According to one embodiment of the invention, the electrochemical anode 202 is a titanium, molybdenum-based electrochemically corrosion resistant, dimensionally stable anode.
In one particular embodiment of the invention, electrochemical anode 202 comprises: a substrate made of a porous (or non-porous) plate and/or a (stretched) wire mesh of titanium or molybdenum-based material; and, a metal oxide electrocatalytic coating overlying the substrate.
In an embodiment according to the invention, the metal oxide electrocatalytic coating is from Ti/RuO2，Ti/SnO2-Sb2O3，Ti/Nb2O5-SnO2，Ti/PbO2，Ti/IrO2The coating is prepared by one method selected from pyrolysis, electrodeposition, sol-gel and other preparation methods.
In one embodiment of the present invention, the electrochemical cathode 206 comprises a porous plate, a non-porous plate, a metal mesh, or a porous plate, a non-porous plate, a mesh, or a carbon-based substrate material such as carbon cloth, carbon paper, graphite fiber film, or carbon film, which is based on nickel or stainless steel, and supports Pt/C, carbon nanotubes, or a nano-powder catalyst of Ni, Raney Ni, Ni-S, Ni-Mo, or Ni-Mo-S.
According to one embodiment of the invention, an ion exchange membrane is provided between the electrochemical anode 202 and the electrochemical cathode 206 of the electrolytic cell 105, as shown in FIG. 2.
When an ion exchange membrane 205 is provided in the cell 105, as shown in figure 2, in one embodiment of the invention, the electrochemical anode 202, the ion exchange membrane 205 and the electrochemical cathode 206 are compacted using first and second cell end plates 201, 231 to form a "zero pole pitch" solid electrolyte cell. Wherein an anode chamber 104 is formed between the first cell end plate 201 and the electrochemical anode 202, having an anode water inlet 211 and an anode water outlet 212. Between the second cell end plate 231 and the electrochemical cathode 206 a cathode chamber 207 is formed having a cathode water inlet 213 and a cathode water outlet 214.
In embodiments of the present invention, the ion exchange membrane 205 may be a proton exchange membrane (e.g., a Nafion membrane) or an anion exchange membrane.
In the wastewater treatment process of the solar-powered high-salinity organic wastewater treatment device according to one embodiment of the invention, the pretreated wastewater is treated at a concentration of 0.01-0.20ml/cm2Min flow rate, continuously entering the anode chamber 202 and the cathode chamber 207 of said electrolytic cell 105 through the anode inlet 211 and the cathode inlet 213, respectively, while passing through the anode current collector 208 and the cathodeElectrolyzing in a constant current charging mode under the action of external direct current (2-4V) applied by the electrode current collector 209; the electrochemical anode 202 is at 5-50mA/cm2Under the current density of (2), an oxidant comprising hydroxyl radicals, chlorine and ozone is generated on the surface of the metal oxide electrocatalytic coating on the anode 202, and soluble organic pollutants and ammonia nitrogen in the wastewater are oxidized on the surface of the electrochemical anode, so that refractory organic matters are mineralized and degraded, and the ammonia nitrogen is nitrified.
After the electrochemical oxidation treatment of the electrolytic cell 105, the wastewater flows out of the electrolytic cell 105 through the anode water outlet 212 and the cathode water outlet 214, and enters the capacitive deionization desalination device 110.
The capacitive deionization desalination device 110 according to one embodiment of the present invention comprises a plurality of sets of capacitive deionization units 301, each operating in parallel.
According to the embodiment of the present invention as shown in fig. 3, each capacitive deionization unit 301 comprises a first end plate 302, a first gasket 303, a first current collector 304, a carbon-based capacitive first electrode 305, a first separator 306, a third gasket 307, a second separator 316, a carbon-based capacitive second electrode 315, a second current collector 314, a second gasket 313, and a second end plate 312, which are arranged in this order. Wherein the third gasket 307 is hollow, and the inner space thereof forms a desalting chamber.
According to one embodiment of the present invention, the first and second end plates 302 and 312 are non-conductive materials for supporting a capacitive deionization unit; the first and second current collectors 304 and 314 (including the tabs 321 and 322) are used for collecting current and are made of electrochemical corrosion resistant materials, such as copper, aluminum, titanium foil or graphite sheet; the first current collector 304 is in substantial contact with the carbon-based capacitive first electrode 305; the second current collector 314 is in substantial contact with the carbon-based capacitive second electrode 315.
According to an embodiment of the present invention, the carbon-based capacitive first electrode 305 and the carbon-based capacitive second electrode 315 are formed with a high specific surface area (100-2Per g of active carbon (or capacitance carbon), conductive carbon black and binder in a certain proportionMixing according to the weight ratio of 8:1:1), heating at high temperature (300 ℃), and hot-pressing into a carbon film with the thickness of 1 mm; according to a specific embodiment, the binder is one selected from polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol and sodium carboxymethyl cellulose.
According to an alternative embodiment of the present invention, the carbon-based capacitive first electrode 305 and the carbon-based capacitive second electrode 315 may also be formed with a high specific surface area (400-2(g), high conductivity (10-100S/cm) carbon aerogel,
according to an alternative embodiment of the present invention, in order to increase the conductivity of the carbon-based capacitor first electrode 305 and the carbon-based capacitor second electrode 315, conductive carbon materials such as carbon nanotubes and graphene may be modified.
According to one embodiment of the present invention, the first membrane 306 and the second membrane 316 are hydrophilic porous membrane materials, such as non-woven fabrics, glass fibers, and the like.
According to an embodiment of the present invention, the first spacer 303, the second spacer 313, and the third spacer 307 are used to seal the carbon-based capacitor first electrode 305 and the carbon-based capacitor second electrode 315, and control the distance between the carbon-based capacitor first electrode 305 and the carbon-based capacitor second electrode 315 to be in the range of 1-3 mm.
The capacitive deionization desalination device 110 adopts a continuous flow operation mode, continuously leads the effluent from one or more electrochemical oxidation electrolytic cells 105 of the electrochemical oxidation device into a desalination chamber inside the hollow third gasket 307 through a water inlet 308 on the hollow third gasket 307, and leads the water treated in the desalination chamber out of a water outlet 309 on the third gasket 307 to be used as the effluent of the capacitive deionization desalination device 110; applying 1.0-1.5V direct current to the carbon-based capacitor first electrode 305 and the carbon-based capacitor second electrode 315 to perform capacitive adsorption deionization, and outputting the effluent of the capacitive deionization desalination device 110 as desalted water 111; when the conductivity of the effluent of the capacitive deionization and desalination device 110 is continuously increased from low to close to the conductivity of the influent, stopping supplying power to the capacitive deionization and desalination device 110, and short-circuiting or reversely switching on direct current to two electrodes of a carbon-based capacitor first electrode 305 and a carbon-based capacitor second electrode 315 of the capacitive deionization and desalination device to release the absorbed ions of the capacitor, and outputting the effluent of the capacitive deionization and desalination device 110 as the concentrated brine 112; when the conductivity of the effluent of the capacitive deionization and desalination device 110 is continuously reduced from high to the conductivity of the inlet water, the direct current of 1.0-1.5V is switched on again to begin desalination; the capacitive deionization desalination device 110 operates in cycles.
In the capacitive deionization (MCDI) desalination apparatus 110, a group of cation 331 and anion exchange membrane 332 can be added between the carbon-based capacitive first electrode 305 and the carbon-based capacitive second electrode 315 to form a Membrane Capacitive Deionization (MCDI) desalination apparatus; conductive resins and fillers such as activated carbon may be added between the MCDI cation and anion exchange membranes to increase desalination and current efficiency.
The solar power supply device 103 is used for supplying power to the electrolytic cell and the capacitive deionization desalination device; renewable solar energy is used as a power supply of the electrolytic cell and the capacitive deionization desalination device, and alternating current-direct current conversion is not needed, so that the electric energy utilization rate is improved.
In accordance with an alternative embodiment of the present invention, to ensure stable operation of the electrolytic cell 105 and capacitive deionization and desalination apparatus 110, a battery 113 is provided to store excess electrical energy and provide the electrical power required for operation of the apparatus during periods of low sunlight. The battery 113 is connected to the solar power unit 103 to receive and store excess electrical energy generated by the solar power unit 103 and to the electrochemical oxidation electrolyzer 105 and the capacitive deionization and desalination unit 110 to provide the electricity required for the operation of the electrochemical oxidation electrolyzer 105 and the capacitive deionization and desalination unit 110 during periods of low sunlight.
Claims (10)
1. A solar-powered high-salinity organic wastewater treatment device is characterized by comprising:
at least one electrochemical oxidation cell (105),
a capacitive deionization desalination device (110),
a solar power supply device (103),
wherein,
each of the electrolytic cells (105) comprises an electrochemical anode (202), an electrochemical cathode (206) and a cell body,
the capacitive deionization and desalination device (110) comprises at least one group of capacitive deionization units (301),
the solar power supply device (103) is used for supplying electric power to the electrolytic cell (105) and the capacitance deionization and desalination device (110) as direct current power supplies of the electrolytic cell and the capacitance deionization and desalination device.
2. The solar powered high salinity organic wastewater treatment plant of claim 1, characterized in that:
each capacitive deionization unit (301) comprises a first end plate (302) for supporting, a first gasket (303), a first current collector (304) for collecting current, a carbon-based capacitive first electrode (305), a first diaphragm (306), a silica gel sealing ring (307) with a desalting chamber, a second diaphragm (316), a carbon-based capacitive second electrode (315), a second current collector (314) for collecting current, a second gasket (313) and a second end plate (312) for supporting, which are arranged in sequence,
each of the electrolysis cells (105) further comprises:
an ion exchange membrane (205) disposed between the electrochemical anode (202) and the electrochemical cathode (206),
a first electrolytic cell end plate (201) and a second electrolytic cell end plate (231) for compressing the electrochemical anode (202), the first silica gel sealing ring (203), the ion exchange membrane (205), the second silica gel sealing ring (204) and the electrochemical cathode (206) to form a compact solid electrolyte electrolytic cell,
an anode chamber (104) formed between the first cell end plate (201) and the electrochemical anode (202) having an anode water inlet (211) and an anode water outlet (212),
a cathode chamber (106) formed between the second cell end plate (231) and the electrochemical cathode (206), having a cathode water inlet (213) and a cathode water outlet (214).
3. The solar powered high salinity organic wastewater treatment plant of claim 2, characterized in that:
the electrochemical anode (202) comprises:
a substrate made of one selected from titanium and molybdenum-based materials and having one selected from a porous plate, a non-porous plate, and a wire mesh; and
a metal oxide electrocatalytic coating overlying the substrate,
wherein,
the metal oxide electrocatalytic coating is prepared from Ti/RuO2，Ti/SnO2-Sb2O3，Ti/Nb2O5-SnO2，Ti/PbO2，Ti/IrO2A coating layer of a selected one of the above,
the metal oxide electrocatalytic coating is prepared by one of the preparation methods of pyrolysis, electrodeposition, sol-gel and the like,
the electrochemical cathode (206) has a form selected from the following forms:
a porous plate, a non-porous plate, a metal mesh, and
porous plate, non-porous plate, and mesh using one material selected from carbon cloth, carbon paper, graphite fiber film, and carbon film as base material,
wherein,
the electrochemical cathode (206) supports a nano powder catalyst, and the nano powder catalyst is at least one selected from Pt/C, carbon nano tube, Ni, Raney Ni, Ni-S, Ni-Mo or Ni-Mo-S nano powder catalyst.
4. The solar powered high salinity organic wastewater treatment plant of claim 2, characterized in that:
the first end plate (302) and the second end plate (312) are made of a non-conductive material,
the first current collector (304) comprises a first tab (321), the second current collector (314) comprises a second tab (322),
the first current collector (304) and the second current collector (314) are made of a material selected from copper, aluminum, titanium foil, graphite sheet,
the first current collector (304) is in intimate contact with a carbon-based capacitive first electrode (305),
the second current collector (314) is in intimate contact with a carbon-based capacitive second electrode (315).
5. The solar powered high salinity organic wastewater treatment plant of any one of claims 2-4, characterized in that:
the first separator (306) and the second separator (316) are hydrophilic porous membranes made of one material selected from a nonwoven fabric and glass fibers,
the first gasket (303), the second gasket (313) and the third gasket (307) form a seal for the first carbon-based capacitor electrode (305) and the second carbon-based capacitor electrode (315), and limit the distance between the first carbon-based capacitor electrode (305) and the second carbon-based capacitor electrode (315) within the range of 1-3 mm.
6. The solar powered high salinity organic wastewater treatment plant of any one of claims 2-4, characterized in that:
the carbon-based capacitive first electrode (305) and the carbon-based capacitive second electrode (315) are made of one material selected from the following materials:
100-1000m2mixing one selected from activated carbon and capacitance carbon with/g specific surface, conductive carbon black and binder at a mass ratio of 8:1:1, heating at 300 deg.C, hot-pressing to obtain carbon film with thickness of 1mm, and
specific surface 400-1100m2Carbon aerogel with the electrical conductivity of 10-100S/cm per gram,
the binder is one selected from polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol and sodium carboxymethyl cellulose,
the first (305) and second (315) carbon-based capacitive electrodes are loaded (see whether the expression "material" is appropriate here) with a conductive carbon material selected from carbon nanotubes and graphene to increase its conductivity,
the ion exchange membrane (205) is one selected from a proton exchange membrane and an anion exchange membrane,
the solar powered high-salt organic wastewater treatment plant further comprises a wastewater pretreatment device connected upstream of the at least one electrochemical oxidation electrolysis cell (105) for removing insoluble suspended particulate matter from the wastewater to be treated.
7. The solar powered high salinity organic wastewater treatment plant of any one of claims 2-4, characterized in that:
the solar-powered high-salinity organic wastewater treatment device comprises a plurality of electrolytic tanks (105) which are arranged in parallel,
the capacitive deionization and desalination device (110) comprises a plurality of groups of capacitive deionization units (301) which are arranged in parallel, and
the capacitive deionization and desalination device (110) further comprises a cation exchange membrane (331) and an anion exchange membrane (332) disposed between the carbon-based capacitive first electrode (305) and the carbon-based capacitive second electrode (315), forming a membrane capacitive deionization and desalination device,
a filler is added between the cation exchange membrane and the anion exchange membrane, and the filler is at least one material selected from conductive resin and activated carbon to increase desalination and current efficiency.
8. The solar powered high salinity organic wastewater treatment plant according to any one of claims 2-4, characterized by further comprising:
and the storage battery (113) is matched with the solar power supply device (103) and is connected to the solar power supply device (103) to receive and store the redundant electric energy generated by the solar power supply device (103) and provide the electric power required by the operation of the electrochemical oxidation electrolytic cell (105) and the capacitance deionization desalination device (110) in the period of lacking sunlight.
9. The method for treating high-salinity organic wastewater based on the solar-powered high-salinity organic wastewater treatment apparatus according to any one of claims 2 to 8, characterized by comprising:
A) continuously introducing the wastewater to be treated into an anode chamber (104) and a cathode chamber (106) of the electrolytic cell (105) through an anode water inlet (211) and a cathode water inlet (213), respectively,
B) electrolyzing the wastewater to be treated in the anode chamber (104) in a constant current charging mode under the action of external direct current (2-4V) applied by an anode current collector (208) and a cathode current collector (209),
C) the wastewater in the anode chamber (104) respectively flows out of the electrolytic cell (105) through an anode water outlet (212) and a cathode water outlet (214) and enters a capacitive deionization and desalination device (110),
D) leading the effluent from the electrochemical oxidation electrolytic tank (105) to enter a desalting chamber inside a silica gel sealing ring (307) through a water inlet (308) on the hollow silica gel sealing ring (307), leading the water treated in the desalting chamber out of a water outlet (309) on the silica gel sealing ring (307) to be used as the effluent of the capacitive deionization desalting device (110),
E) applying 1.0-1.5V direct current to the first electrode (305) and the second electrode (315) of the carbon-based capacitor to perform capacitive adsorption deionization, outputting the effluent of the capacitive deionization desalination device (110) as desalted water,
F) when the conductivity of the effluent of the capacitive deionization and desalination device (110) is continuously increased from low to close to the conductivity of the influent, the power supply to the capacitive deionization and desalination device (110) is stopped, the two electrodes of the first electrode (305) and the second electrode (315) of the carbon-based capacitor of the capacitive deionization and desalination device are in short circuit and/or are in reverse direct current connection, the capacitor is released to adsorb ions, and the effluent of the capacitive deionization and desalination device (110) is output as concentrated brine (112),
G) when the conductivity of the outlet water of the capacitive deionization and desalination device (110) is continuously reduced from high to the conductivity of the inlet water, the direct current of 1.0-1.5V is switched on again for desalination,
H) repeating the above steps E) to G).
10. The method of claim 9, wherein:
the flow rate of the wastewater in the step A) is 0.01-0.20ml/cm2The time of the second-hand operation was,
the current density of the electrochemical anode (202) is 5-50mA/cm2The range of the total amount of the active ingredients,
wherein,
an oxidant comprising hydroxyl radicals, chlorine and ozone is generated on the surface of the metal oxide electrocatalytic coating on the anode (202), and soluble organic pollutants and ammonia nitrogen in the wastewater are oxidized on the surface of the electrochemical anode, so that refractory organic matters are mineralized and degraded, and the ammonia nitrogen is nitrified.
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