CN110902781A - Device and method for treating phosphorus-containing wastewater and recycling phosphorus resources by iron-air battery - Google Patents
Device and method for treating phosphorus-containing wastewater and recycling phosphorus resources by iron-air battery Download PDFInfo
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- CN110902781A CN110902781A CN201911287298.8A CN201911287298A CN110902781A CN 110902781 A CN110902781 A CN 110902781A CN 201911287298 A CN201911287298 A CN 201911287298A CN 110902781 A CN110902781 A CN 110902781A
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 111
- 239000011574 phosphorus Substances 0.000 title claims abstract description 111
- 239000002351 wastewater Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000004064 recycling Methods 0.000 title description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000003792 electrolyte Substances 0.000 claims abstract description 75
- 229910052742 iron Inorganic materials 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000012528 membrane Substances 0.000 claims abstract description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011780 sodium chloride Substances 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 35
- 238000003860 storage Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 4
- -1 ferrous iron ions Chemical class 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001448 ferrous ion Inorganic materials 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 229910052683 pyrite Inorganic materials 0.000 abstract 1
- 238000007789 sealing Methods 0.000 description 14
- 239000004033 plastic Substances 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 238000010170 biological method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- 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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46176—Galvanic cells
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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- 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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46119—Cleaning the electrodes
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- 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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
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- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a device and a method for treating phosphorus-containing wastewater and recovering phosphorus resources by an iron-air battery, wherein a positive electrode and a negative electrode respectively adopt an iron electrode and an air electrode with lower cost, the wastewater containing phosphate is added into an anode chamber, and a sodium chloride solution is added into a cathode chamber as electrolyte; the cathode chamber and the anode chamber are separated by a proton exchange membrane and are connected by an external lead. The potential difference enables the iron anode to lose electrons, and generated ferrous ions react with phosphate in the anolyte to generate iron pyrite; the electrons reach the air electrode through the external lead, and oxygen in the air reacts with the electrons received by the cathode to generate water; the proton inside the battery moves through the proton exchange membrane to form a loop, and an open-circuit voltage of 1.2V can be generated in an external circuit. The invention takes ferrous ions generated in situ by the iron electrode as a phosphorus removing agent, realizes the phosphorus removal of the wastewater on the premise of not introducing other impurity ions, and can also recover phosphorus resources and electric energy in the wastewater.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a device and a method for treating phosphorus-containing wastewater and recycling phosphorus resources by using an iron-air battery.
Background
Phosphorus is one of the main causes of water eutrophication, and wastewater phosphorus removal is an effective way for preventing and treating water eutrophication. The wastewater dephosphorization technology is mainly divided into two main types of chemical method and biological method. The biological method is widely applied due to the advantages of economy, effectiveness, environmental friendliness and the like, but also has the problems of long reaction time, large equipment floor area, difficult sludge treatment and the like; the chemical phosphorus removal method has the advantages of economy, high efficiency, simple and convenient operation, reliable effect, difficult influence of the quality of wastewater and the like, and is popularized and applied. Ferrous salt is commonly used as a flocculating agent for chemical dephosphorization of wastewater, and has the advantages of high efficiency, safety and the like. The method can reasonably control the phosphorus removal condition of the ferrous salt to generate a high-value mineral substance containing phosphorus and iron, namely the vivianite. The high-crystallinity hematite can be used for manufacturing ornaments such as crystals, and the powdery hematite can be used as farmland fertilizer or drawing dye.
Phosphorus resources are distributed unevenly on the earth and have limited reserves, and as the population grows and the living standard of human beings is continuously improved, the demand of the society for phosphorus is higher and higher. Therefore, how to change the 'phosphorus removal' in the wastewater into 'phosphorus recycling' becomes the development trend of sewage phosphorus removal, and a novel green and environment-friendly phosphorus resource recovery technology needs to be searched urgently.
Disclosure of Invention
Aiming at the phosphorus-containing wastewater, the invention provides a device and a method for treating the phosphorus-containing wastewater and recovering phosphorus resources by using an iron-air battery, aiming at solving the problems in the prior art.
In order to achieve the purpose, the invention adopts the following specific scheme:
a device for treating phosphorus-containing wastewater and recovering phosphorus resources by using an iron-air battery comprises a cathode chamber and an anode chamber, wherein a proton exchange membrane is arranged between one side of the cathode chamber and one side of the anode chamber and is in sealed connection with the cathode chamber, an air electrode is arranged on the other side of the cathode chamber, an electrolyte circulating system of the cathode chamber is connected onto the cathode chamber, and a lead is connected onto the air electrode and extends to the outside of the cathode chamber;
the anode chamber is provided with an anode chamber water inlet, an iron electrode and a phosphorus removal product discharge port, the phosphorus removal product discharge port is positioned at the bottom of the anode chamber, the iron electrode is arranged in the anode chamber, and the iron electrode is connected with a lead which extends to the outside of the anode chamber.
The electrolyte circulating system of the cathode chamber comprises an electrolyte inlet, a water inlet pipe, an electrolyte storage tank, a connecting pipe, a circulating pump, a water outlet pipe and an electrolyte outlet, wherein the electrolyte inlet is arranged at the lower part of one side of the cathode chamber, and the electrolyte outlet is arranged at the upper part of the other side of the cathode chamber; the electrolyte inlet is connected with the electrolyte liquid storage tank through a water inlet pipe, the water inlet of the circulating pump is connected with the electrolyte liquid storage tank through a connecting pipe, and the water outlet of the circulating pump is connected with the electrolyte outlet through a water outlet pipe.
The distance from an electrolyte inlet to the bottom of the electrolyte circulating system in the cathode chamber is 1/3 the total height of the cathode chamber, the distance from an electrolyte outlet to the bottom of the electrolyte circulating system in the cathode chamber is 2/3 the total height of the cathode chamber, and the ratio of the inner diameter of the electrolyte inlet to the inner diameter of the electrolyte outlet is 1: 1.
An external blade clamping groove is embedded in the upper part of the anode chamber, an iron electrode passes through the external blade clamping groove and is suspended in the middle of the anode chamber, and the upper end of the iron electrode is connected with a lead; two blades are arranged in the external blade clamping groove, the two blades are arranged in a V shape, and the iron electrode penetrates through the two blades.
The bottom of the anode chamber is provided with a dephosphorization product collecting hopper, and the outlet of the dephosphorization product collecting hopper is used as a dephosphorization product outlet.
The volume ratio of the cathode chamber to the anode chamber is 1: 1.
Phosphorus-containing wastewater is added into the anode chamber, the concentration of the phosphorus-containing wastewater is 5-1000mg-p/L, and 1-3mol/L sodium chloride solution is adopted as electrolyte in the cathode chamber.
Every 3.5-4cm3The anode chambers are correspondingly configured to be 1-1.5cm2The iron electrode of (4); each 1.1-1.5cm3The cathode chamber is correspondingly arranged by 1-1.2cm2The air electrode of (1).
Each 1.1-1.5cm3The cathode chamber is correspondingly arranged by 1-1.2cm2The proton exchange membrane of (1).
A method for treating phosphorus-containing wastewater and recovering phosphorus resources by an iron-air battery comprises the following steps:
phosphate-containing wastewater enters the anode chamber from a water inlet of the anode chamber to be used as anolyte;
adding catholyte into the cathode chamber;
connecting a lead connected to the iron electrode with a lead connected to the air electrode or with an electric load;
losing electrons from an iron electrode in the anode chamber to generate soluble ferrous iron, and enabling soluble ferrous iron ions to enter the anolyte and react with phosphate ions in the anolyte to generate a ferrocyanide precipitate; the vivianite is discharged through a dephosphorization product discharge port;
electrons lost from the iron electrode are transferred to the air electrode;
the catholyte accepts electrons on the air electrode;
the proton exchange membrane separates the anode chamber from the cathode chamber, and the charge balance of the anode chamber and the cathode chamber is maintained through proton exchange.
The invention has the beneficial effects that:
the device for treating phosphorus-containing wastewater and recovering phosphorus resources by using the iron-air battery utilizes cheap and easily available zero-valent iron as the anode, so that the phosphorus removal cost of the wastewater is reduced; the phosphorus-containing wastewater is used as anolyte, electrons are lost from an iron electrode, and generated ferrous ions react with phosphate in the anolyte to generate iron cyanite, so that the recycling of phosphorus resources in the phosphorus-containing wastewater is realized, and waste is changed into valuable; meanwhile, the iron electrode is connected with a lead, the air electrode is connected with a lead, and when the air electrode is used, the two leads are connected to a power consumption load or an electric energy recovery device, so that the purpose of power generation can be realized; the electrolyte circulating system of the cathode chamber ensures that the concentration of catholyte in the cathode chamber is relatively uniform, and ensures the reaction efficiency and stable power generation capacity.
Furthermore, after the iron anode reacts for a period of time, the synthesized iron cyanite can cover the surface of the iron cyanite, so that the iron cyanite is passivated, the electron losing capability of the iron anode is reduced, the blade clamping groove is arranged to conveniently clear the surface, and the stable electricity generating performance is ensured.
The method for treating the phosphorus-containing wastewater and recovering the phosphorus resource by the iron-air battery can utilize the zero-valent iron to treat the phosphate-containing wastewater to obtain the vivianite, the zero-valent iron is cheap and easy to obtain, so the cost is low, the obtained vivianite realizes the recycling of the phosphorus resource in the wastewater, the waste is changed into valuable, and simultaneously the electric energy can be obtained in the wastewater treatment process.
Drawings
FIG. 1 is an overall view of an apparatus for treating phosphorus-containing wastewater and recovering phosphorus resources by using an iron-air battery according to the present invention;
FIG. 2 is a sectional view of an apparatus for treating phosphorus-containing wastewater and recovering phosphorus resources by using an iron-air battery according to the present invention;
FIG. 3 is an overall view of the cathode chamber of the apparatus for treating wastewater containing phosphorus and recovering phosphorus resources by using the iron-air battery according to the present invention;
FIG. 4 is a sectional view of a cathode chamber of an apparatus for treating wastewater containing phosphorus and recovering phosphorus resources by using an iron-air battery according to the present invention;
FIG. 5 is a cross-sectional view of an anode chamber of a device for treating phosphorus-containing wastewater and recovering phosphorus resources by using an iron-air battery according to the present invention.
In the figure: a cathode chamber A and an anode chamber B; the device comprises a first sealing cover 1, a sealing gasket 2, an air electrode 3, an external lead port I4, a cathode chamber electrolyte circulating system 5, an electrolyte inlet 5-1, a water inlet pipe 5-2, an electrolyte storage tank 5-3, a connecting pipe 5-4, a circulating pump 5-5, a water outlet pipe 5-6 and an electrolyte outlet 5-7; a proton exchange membrane 6; a water inlet 7 of the anode chamber, an external lead port II 8, an external blade clamping groove 9, a blade 9-1, an iron electrode 10, a second sealing cover 11, a dephosphorization product discharge port 12 and a dephosphorization product collecting hopper 13; the device comprises a battery bracket 14, a shell fixing screw 15, an external lead 16 and an electric signal acquisition system 17.
Detailed Description
The invention is further described with reference to the following detailed description of the invention and the accompanying drawings. The preferred embodiments may be combined in any combination, unless otherwise specified or conflicting.
As shown in fig. 1 and 2, the apparatus for treating phosphorus-containing wastewater and recovering phosphorus resources by using an iron-air battery according to the present invention comprises a cathode chamber a and an anode chamber B, wherein a proton exchange membrane 6 is disposed between one side of the cathode chamber a and one side of the anode chamber B and hermetically connected to each other, an air electrode 3 is disposed on the other side of the cathode chamber a, a cathode chamber electrolyte circulation system 5 is connected to the cathode chamber a, and a lead wire is connected to the air electrode 3 and extends to the outside of the cathode chamber a; the anode chamber B is provided with an anode chamber water inlet 7, an iron electrode 10 and a phosphorus removal product discharge port 12, the phosphorus removal product discharge port 12 is positioned at the bottom of the anode chamber B, the iron electrode 10 is arranged in the anode chamber B, and the iron electrode 10 is connected with a lead which extends to the outside of the anode chamber B.
As a preferred embodiment of the present invention, as shown in fig. 1 to 4, the electrolyte circulation system 5 of the cathode chamber comprises an electrolyte inlet 5-1, a water inlet pipe 5-2, an electrolyte tank 5-3, a connecting pipe 5-4, a circulating pump 5-5, a water outlet pipe 5-6 and an electrolyte outlet 5-7, wherein the electrolyte inlet 5-1 is provided at the lower part of one side of the cathode chamber a, and the electrolyte outlet 5-7 is provided at the upper part of the other side of the cathode chamber a; an electrolyte inlet 5-1 is connected with an electrolyte liquid storage tank 5-3 through a water inlet pipe 5-2, a water inlet of a circulating pump 5-5 is connected with the electrolyte liquid storage tank 5-3 through a connecting pipe 5-4, and a water outlet of the circulating pump 5-5 is connected with an electrolyte outlet 5-7 through a water outlet pipe 5-6.
As a preferred embodiment of the present invention, as shown in fig. 2 and 5, an external blade slot 9 is embedded in the upper portion of the anode chamber B, an iron electrode 10 passes through the external blade slot 9 and is suspended in the middle of the anode chamber B, and the upper end of the iron electrode 10 is connected with a lead; two blades are arranged in the external blade clamping groove 9, the two blades are arranged in a V shape, and the iron electrode 10 penetrates through the two blades.
As a preferred embodiment of the present invention, as shown in FIG. 1, FIG. 2 and FIG. 5, a phosphorus removal product collecting hopper 13 is provided at the bottom of the anode chamber B, and the outlet of the phosphorus removal product collecting hopper 13 is used as a phosphorus removal product discharge port 12.
As a preferred embodiment of the present invention, as shown in fig. 1 and fig. 2, the lead wire connected to the air electrode 3 and the lead wire connected to the iron electrode 10 may be directly connected to each other, or connected to an electric appliance, or connected to an electric energy collector, or connected to an electric signal acquisition system 17.
In the device for treating phosphorus-containing wastewater and recovering phosphorus resources by using the iron-air battery, the anode and the cathode are respectively manufacturedThe iron electrode and the air electrode are low in cost, wastewater containing phosphate is added into an anode chamber, and 1mol/L sodium chloride solution is added into a cathode chamber to serve as electrolyte; the cathode chamber and the anode chamber are separated by a proton exchange membrane, and the cathode chamber and the anode chamber are connected by an external lead to form a primary battery system. The potential difference between the iron anode and the air cathode causes the iron anode to lose electrons, and the generated ferrous ions react with phosphate in the anolyte to generate ferrocyanite (Fe)3(PO4)2·8H2O); the electrons reach the air cathode through an external lead, oxygen in the air reaches the catalyst layer through the collection of the gas collection layer, and the oxygen reacts with the electrons received by the cathode to generate water under the action of the Pt/C catalyst; the proton inside the battery moves through the proton exchange membrane to form a loop, and an open-circuit voltage of 1.2V can be generated in an external circuit. The device takes ferrous ions generated in situ by the iron electrode as a phosphorus removal agent, realizes the phosphorus removal of the wastewater on the premise of not introducing other impurity ions, and can also recover phosphorus resources and electric energy in the wastewater.
Examples
As shown in fig. 1 to 5, the device for treating phosphorus-containing wastewater and recovering phosphorus resources by using the iron-air battery of the embodiment comprises a cathode chamber a, an anode chamber B and external connecting equipment, wherein the cathode chamber a and the anode chamber B are hollow cavities; the cathode chamber A is connected with a hollow plastic sealing cover, a sealing gasket 2, an air electrode 3, an external lead port I4 and a cathode chamber electrolyte circulating system 5, and the cathode chamber electrolyte circulating system 5 comprises an electrolyte inlet 5-1, a water inlet pipe 5-2, an electrolyte storage tank 5-3, a connecting pipe 5-4, a circulating pump 5-5, a water outlet pipe 5-6 and an electrolyte outlet 5-7; the cathode chamber A and the anode chamber B are in mass transfer through a proton exchange membrane 6, and the cathode chamber A and the anode chamber B are in sealed connection through a sealing gasket 2; an anode chamber water inlet 7, an external lead port II 8, an external blade clamping groove 9, an iron electrode 10, a solid plastic sealing cover, a dephosphorization product discharge port 12 and a dephosphorization product collecting hopper 13 are arranged on the anode chamber B; the external connecting equipment comprises a battery bracket 14, a shell fixing screw 15, an external lead 16 and an electric signal acquisition system 17.
As shown in fig. 1 and fig. 2, the air electrode 3 is arranged at the left side of the inner cavity of the cathode chamber a, the right side surface of the cathode chamber a is sealed by a hollow plastic sealing cover and a sealing gasket 2, an external lead port i 4 is arranged at the upper part of the right side of the cathode chamber a, and a cathode chamber electrolyte circulating system 5 is arranged at the bottom of the cathode chamber a; the upper end of the air electrode 3 is connected with an external lead 16; an external lead 16 extends into the cathode chamber through an external lead port I4 and is connected with the air electrode 3; an electrolyte inlet 5-1 in an electrolyte circulating system 5 of the cathode chamber is arranged below one side of the cathode chamber A, and an electrolyte outlet 5-6 is arranged above the other side of the cathode chamber; an electrolyte storage tank 5-3 and a circulating pump 5-4 are arranged at the bottommost part of the device; the electrolyte circulation is completed by connecting the water inlet pipe 5-2, the connecting pipe 5-4 and the water outlet pipe 5-5 in series.
As shown in fig. 1 and 2, a water inlet 7 of the anode chamber, an external lead port ii 8, an external blade clamping groove 9 and a sealing gasket 2 and a solid plastic cover are arranged on the top of the anode chamber B, the left side surface of the anode chamber B is sealed by the sealing gasket 2 and the solid plastic cover, a phosphorus removal product collecting hopper 13 is arranged on the lower part of the anode chamber B, and an outlet of the phosphorus removal product collecting hopper 13 is used as a phosphorus removal product outlet 12; the external blade clamping groove 9 is embedded in the upper part of the anode chamber B; the iron electrode 10 passes through the external blade clamping groove 9 and is hung in the middle of the anode chamber, and the upper end of the iron electrode 10 is connected with an external lead 16; an external lead 16 extends into the anode chamber through an external lead port II 8 and is connected with the iron electrode 10; the upper end (i.e. the big end) of the dephosphorization product collecting hopper 13 is connected with the anode chamber reaction area.
The air electrode 3 is connected with the iron electrode 10 through an external lead 16, and an electric signal acquisition system 17 is arranged on the external lead 16; a proton exchange membrane 6 for exchanging substances is arranged between the cathode chamber and the anode chamber; the cathode chamber A, the anode chamber B, the sealing gasket 2, the hollow plastic sealing cover and the solid plastic sealing cover are screwed by four fixing screws 15 and connected into an integral structure, and the bottom of the integral structure is connected with the battery bracket 14 to keep stable.
The sizes and proportions of the components can be set according to actual conditions. In this example, the cathode chamber and the anode chamber have the same specification, the same volume and the volume ratio of 1: 1. 5-1000mg-p/L of phosphorus-containing wastewater can be added into the anode chamber B, and 1mol/L of sodium chloride solution is adopted as electrolyte in the cathode chamber A; the volumes of liquid in the anode chamber B and the cathode chamber A are the same, and the liquid volume accounts for 90% of the volume of each chamber. The external blade clamping groove 9 is internally provided withThe blades embedded in the upper part of the anode chamber B form a V-shaped structure, and the inclination angle of each blade is 45 degrees; the two blades have the same specification, the length-width ratio of the two blades is 2:1, and the horizontal distance between the bottoms of the two blades at two sides is consistent with the thickness of the iron electrode. In the electrolyte circulating system of the cathode chamber, the distance from an electrolyte inlet to the bottom of the electrolyte circulating system is 1/3 of the total height of the cathode chamber, the distance from an electrolyte outlet to the bottom of the electrolyte circulating system is 2/3 of the total height of the cathode chamber, and the ratio of the inner diameter of the electrolyte inlet to the inner diameter of the electrolyte outlet is 1: 1. The iron electrode is a square iron sheet which is completely immersed in the phosphorus-containing wastewater, and the ratio of the surface area to the anode chamber volume is 1cm2:3.5cm3(ii) a The air electrode was a circular pellet made of a combination of a carbon-based layer, a diffusion layer and a catalytic layer, completely immersed in a sodium chloride electrolyte solution, and had a surface area to cathode chamber volume ratio of 1cm2:1.1cm3. A phosphorus removal product collecting hopper and a phosphorus removal product discharge port are arranged at the bottom of the anode chamber; the inclination angles of the phosphorus removal product collecting hoppers are both 60 degrees, and the ratio of the inner diameter of the phosphorus removal product discharge port to the inner diameter of the water inlet of the anode chamber is 1: 1; the ratio of the surface area of the phosphorus removal product discharge port to the volume of the phosphorus removal product collecting hopper is 1:3.5, and the height of the phosphorus removal product collecting hopper is 1/3 of the total height of the anode chamber. The cathode chamber and the anode chamber exchange substances between the cathode chamber and the anode chamber through a proton exchange membrane, and the ratio of the surface area of the proton exchange membrane to the volume of the cathode chamber is 1cm2:1.1cm3. The pH value of the anolyte is 4-9, the oxidation-reduction potential is-300-600 mv, the Fe/P is more than 1.5, and the generation of the vivianite can be observed on the surfaces of a dephosphorization product collecting hopper and an iron electrode. Through tests, the dimensional proportion and the parameters can well fulfill the test aim of the invention.
The device for treating phosphorus-containing wastewater and recovering phosphorus resources by using the iron-air battery can be made of plastics, and the working process is as follows: phosphate-containing wastewater enters the anode chamber from a water inlet 7 of the anode chamber to be used as anolyte; the iron electrode 10 in the anode chamber loses electrons to generate soluble ferrous iron, and ferrous iron ions enter the anolyte and react with phosphate ions in the anolyte to generate a ferrocyanide precipitate; the vivianite is collected by a phosphorous removal product collecting hopper 13 and discharged from a phosphorous removal product discharge port 12. The lost electrons of the iron electrode 10 of the anode chamber are transmitted to the air electrode 3 of the cathode chamber through an external lead 16, the current is formed in an external circuit, and the data acquisition is carried out by an electric signal collection system 17. Sodium chloride solution enters the cathode chamber through an electrolyte inlet 5-1 in an electrolyte circulating system 5 to serve as catholyte, oxygen enters the cathode chamber as an active substance to serve as an electricity consuming substance, and electrons are received on the air electrode 3 to generate water. The proton exchange membrane 6 separates the anode chamber from the cathode chamber, so that on one hand, charge balance of the anode chamber and the cathode chamber is maintained through proton exchange, and on the other hand, oxygen in the cathode chamber is isolated, and the anaerobic environment of the anode chamber is ensured.
The invention has the following characteristics:
1) the zero-valent iron is cheap and easy to obtain, so that the phosphorus removal cost of the wastewater is reduced; 2) the reaction period is short, the phosphorus-containing wastewater can be efficiently treated, and phosphorus resources can be recovered in a vivianite form; 3) the arrangement of the electrolyte circulating system and the blade clamping groove ensures the stable electricity generating performance, and the open-circuit voltage can reach 1.2V.
Claims (10)
1. The device for treating phosphorus-containing wastewater and recovering phosphorus resources by using the iron-air battery is characterized by comprising a cathode chamber (A) and an anode chamber (B), wherein a proton exchange membrane (6) is arranged between one side of the cathode chamber (A) and one side of the anode chamber (B) and is in sealed connection with the cathode chamber (A), an air electrode (3) is arranged on the other side of the cathode chamber (A), a cathode chamber electrolyte circulating system (5) is connected onto the cathode chamber (A), and a lead wire is connected onto the air electrode (3) and extends to the outside of the cathode chamber (A);
the anode chamber (B) is provided with an anode chamber water inlet (7), an iron electrode (10) and a phosphorus removal product discharge port (12), the phosphorus removal product discharge port (12) is positioned at the bottom of the anode chamber (B), the iron electrode (10) is arranged in the anode chamber (B), and the iron electrode (10) is connected with a lead which extends to the outside of the anode chamber (B).
2. An apparatus for treating phosphorus-containing wastewater and recovering phosphorus resources by an iron-air battery as defined in claim 1, wherein the electrolyte circulation system (5) of the cathode chamber comprises an electrolyte inlet (5-1), a water inlet pipe (5-2), an electrolyte tank (5-3), a connection pipe (5-4), a circulation pump (5-5), a water outlet pipe (5-6) and an electrolyte outlet (5-7), the electrolyte inlet (5-1) is provided at a lower portion of one side of the cathode chamber (a), and the electrolyte outlet (5-7) is provided at an upper portion of the other side of the cathode chamber (a); an electrolyte inlet (5-1) is connected with an electrolyte liquid storage tank (5-3) through a water inlet pipe (5-2), a water inlet of a circulating pump (5-5) is connected with the electrolyte liquid storage tank (5-3) through a connecting pipe (5-4), and a water outlet of the circulating pump (5-5) is connected with an electrolyte outlet (5-7) through a water outlet pipe (5-6).
3. An apparatus for treating phosphorus-containing wastewater and recovering phosphorus resources by using an iron-air battery as claimed in claim 2, wherein the distance from the electrolyte inlet (5-1) to the bottom of the electrolyte circulation system (5) in the cathode chamber is 1/3, the distance from the electrolyte outlet (5-7) to the bottom of the cathode chamber is 2/3, and the ratio of the inner diameter of the electrolyte inlet (5-1) to the inner diameter of the electrolyte outlet (5-7) is 1: 1.
4. The device for treating phosphorus-containing wastewater and recovering phosphorus resources by using the iron-air battery as claimed in claim 1, wherein an external blade clamping groove (9) is embedded in the upper part of the anode chamber (B), the iron electrode (10) passes through the external blade clamping groove (9) and is suspended in the middle of the anode chamber (B), and the upper end of the iron electrode (10) is connected with a lead; two blades are arranged in the external blade clamping groove (9), the two blades are arranged in a V shape, and the iron electrode (10) penetrates through the two blades.
5. The apparatus for treating phosphorus-containing wastewater and recovering phosphorus resources by using an iron-air battery as claimed in claim 1, wherein a phosphorus removal product collecting hopper (13) is arranged at the bottom of the anode chamber (B), and the outlet of the phosphorus removal product collecting hopper (13) is used as a phosphorus removal product discharge port (12).
6. An apparatus for treating phosphorus-containing wastewater and recovering phosphorus resources by an iron-air battery as set forth in claim 1, wherein the volume ratio of the cathode chamber (A) to the anode chamber (B) is 1: 1.
7. The apparatus for treating phosphorus-containing wastewater and recovering phosphorus resources of an iron-air battery as claimed in claim 1, wherein the phosphorus-containing wastewater is supplied to the anode compartment (B) at a concentration of 5 to 1000mg-p/L, and a sodium chloride solution is used as an electrolyte in the cathode compartment (A) at a concentration of 1 to 3 mol/L.
8. The apparatus for treating phosphorus-containing wastewater and recovering phosphorus resources of an iron-air battery as claimed in claim 1, wherein the concentration of phosphorus in the wastewater is 3.5-4cm3The anode chamber (B) is correspondingly configured to be 1-1.5cm2The iron electrode (10); each 1.1-1.5cm3The cathode chamber (A) is correspondingly configured to be 1-1.2cm2The air electrode (3).
9. The apparatus for treating phosphorus-containing wastewater and recovering phosphorus resources of an iron-air battery as claimed in claim 1, wherein the concentration of phosphorus in the wastewater is 1.1-1.5cm3The cathode chamber (A) is correspondingly configured to be 1-1.2cm2The proton exchange membrane (6).
10. A method for treating phosphorus-containing wastewater and recovering phosphorus resources by an iron-air battery, which is characterized by comprising the following steps based on the device of any one of claims 1 to 9:
phosphate-containing wastewater enters an anode chamber (B) from a water inlet (7) of the anode chamber to be used as anolyte;
adding catholyte into the cathode chamber (A);
connecting a lead connected with the iron electrode (10) with a lead connected with the air electrode (3) or with an electric load;
the iron electrode (10) in the anode chamber (B) loses electrons to generate soluble ferrous iron, and soluble ferrous iron ions enter the anolyte and react with phosphate ions in the anolyte to generate a ferrocyanide precipitate; the vivianite is discharged through a dephosphorization product discharge port (12);
the electron lost by the iron electrode (10) is transferred to the air electrode (3);
the catholyte accepts electrons on the air electrode (3);
the proton exchange membrane (6) separates the anode chamber (B) from the cathode chamber (A), and the charge balance of the anode chamber (B) and the cathode chamber (A) is maintained through proton exchange.
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| CN113023702A (en) * | 2021-03-05 | 2021-06-25 | 北京工业大学 | Sludge phosphorus recovery method for synthesizing vivianite by adding sponge iron as seed crystal |
| CN113060799A (en) * | 2021-03-19 | 2021-07-02 | 北京交通大学 | Self-water-absorption self-power-generation type water treatment device and method based on sandwich structure electrode |
| CN114291873A (en) * | 2022-01-27 | 2022-04-08 | 西安建筑科技大学 | Device and method for treating anaerobic digestion wastewater and recycling nitrogen and phosphorus resources by continuous operation of magnesium-air battery |
| CN114804304A (en) * | 2022-05-06 | 2022-07-29 | 泉州师范学院 | Method for recovering phosphorus in sewage by electrolysis |
| CN114835346A (en) * | 2022-05-27 | 2022-08-02 | 北控水务(中国)投资有限公司 | Equipment and process for recovering carbon and phosphorus in sewage |
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| CN114291873A (en) * | 2022-01-27 | 2022-04-08 | 西安建筑科技大学 | Device and method for treating anaerobic digestion wastewater and recycling nitrogen and phosphorus resources by continuous operation of magnesium-air battery |
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| CN114835346B (en) * | 2022-05-27 | 2023-04-07 | 北控水务(中国)投资有限公司 | Equipment and process for recovering carbon and phosphorus in sewage |
| CN115490308A (en) * | 2022-10-25 | 2022-12-20 | 北控水务(中国)投资有限公司 | Reverse osmosis concentrated water regeneration treatment equipment and method |
| CN115490308B (en) * | 2022-10-25 | 2023-11-10 | 北控水务(中国)投资有限公司 | Reverse osmosis concentrated water regeneration treatment equipment and method |
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