CN114291873A - Device and method for treating anaerobic digestion wastewater and recycling nitrogen and phosphorus resources by continuous operation of magnesium-air battery - Google Patents
Device and method for treating anaerobic digestion wastewater and recycling nitrogen and phosphorus resources by continuous operation of magnesium-air battery Download PDFInfo
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- CN114291873A CN114291873A CN202210101482.4A CN202210101482A CN114291873A CN 114291873 A CN114291873 A CN 114291873A CN 202210101482 A CN202210101482 A CN 202210101482A CN 114291873 A CN114291873 A CN 114291873A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000002351 wastewater Substances 0.000 title claims abstract description 73
- 230000029087 digestion Effects 0.000 title claims abstract description 62
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 45
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 45
- 239000011574 phosphorus Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000004064 recycling Methods 0.000 title description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000011777 magnesium Substances 0.000 claims abstract description 67
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 67
- 238000005341 cation exchange Methods 0.000 claims abstract description 31
- 239000012528 membrane Substances 0.000 claims abstract description 31
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 26
- 229910052567 struvite Inorganic materials 0.000 claims abstract description 21
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 15
- 239000010452 phosphate Substances 0.000 claims abstract description 14
- 239000011780 sodium chloride Substances 0.000 claims abstract description 13
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 91
- 239000007788 liquid Substances 0.000 claims description 41
- 239000000047 product Substances 0.000 claims description 35
- 238000003860 storage Methods 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 238000007789 sealing Methods 0.000 claims description 17
- -1 ammonium ions Chemical class 0.000 claims description 12
- 239000010802 sludge Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 4
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims 1
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 5
- 150000001768 cations Chemical class 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 239000011521 glass Substances 0.000 description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 229920005372 Plexiglas® Polymers 0.000 description 5
- 238000011084 recovery Methods 0.000 description 3
- 229910017958 MgNH Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
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Abstract
The invention discloses a device and a method for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources by continuous operation of a magnesium-air batteryDigesting the wastewater, and adding a sodium chloride solution into the anode chamber as an electrolyte; the negative chamber and the positive chamber are separated by a cation exchange membrane and are connected by an external lead. The magnesium anode loses electrons due to the potential difference, and the generated magnesium ions pass through a cation exchange membrane to react with ammonium radicals and phosphate in the anolyte to generate struvite; electrons reach the air electrode through the external lead, and oxygen in the air receives the electron reaction to generate OH‑(ii) a The magnesium ions and other cations in the battery pass through the cation exchange membrane to form a loop, and an open-circuit voltage of 1.3V can be generated in an external circuit. The method takes magnesium ions generated in situ by the magnesium electrode as a phosphorus removal agent, realizes nitrogen and phosphorus removal of the wastewater on the premise of not introducing other impurity ions, and can also recover nitrogen and phosphorus resources and electric energy in the wastewater.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a device and a method for treating anaerobic digestion wastewater and recycling nitrogen and phosphorus resources by continuous operation of a magnesium-air battery.
Background
Nitrogen and phosphorus are indispensable elements in the organism, and are the basis for the survival of all organisms. At present, nitrogen and phosphorus resources in the world are in shortage, and if a large amount of nitrogen and phosphorus contained in the wastewater is not removed in time, eutrophication of a water body is caused, so that the removal and recovery of the nitrogen and phosphorus in the wastewater become a current research hotspot. There are many methods for removing nitrogen and phosphorus from wastewater: biological methods, chemical precipitation methods, and electrochemical methods. The traditional biological method transfers phosphorus in the wastewater into sludge, converts ammonia nitrogen, nitrate and the like into nitrogen and releases the nitrogen into the air, and although the removal of nitrogen and phosphorus is completed, nitrogen and phosphorus resources are not recovered. The chemical precipitation method is to add magnesium salt into the wastewater on the basis of adjusting the alkalinity of the wastewater to form struvite precipitate, and although nitrogen and phosphorus resources are recovered in the process in the form of struvite, new impurity ions are introduced by adding the magnesium salt. The electrochemical method can form struvite sediment under the condition of not introducing other impurity ions, but consumes a large amount of electric energy in the process.
Disclosure of Invention
Aiming at anaerobic digestion wastewater, the invention provides a device and a method for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources by continuous operation of a magnesium-air battery, aiming at the problems in the prior art, the invention utilizes a magnesium electrode to realize the transfer of electrons from an anode to a cathode and generate electric energy for utilization; the magnesium anode loses electrons, and the generated soluble divalent magnesium passes through the cation exchange membrane and then reacts with ammonium radicals and phosphate of the cathode to generate struvite, so that the nitrogen and phosphorus removal of the wastewater is realized, and nitrogen and phosphorus resources are recovered.
In order to achieve the purpose, the invention adopts the following specific technical scheme:
a magnesium-air battery continuously operates and processes the apparatus of anaerobic digestion waste water and reclaiming nitrogen phosphorus resource, including cathode chamber, anode chamber, product collecting hopper and waste water circulation system, there are connected passways between anode chamber and the cathode chamber, there are cation exchange membranes in the passway; an air cathode is arranged in an inner cavity of the cathode chamber, a cathode chamber water inlet and a cathode chamber water outlet are arranged on the cathode chamber, and the cathode chamber water inlet and the cathode chamber water outlet are connected with a wastewater circulating system; the product collecting hopper is arranged at the bottom of the cathode chamber, and the bottom of the product collecting hopper is provided with a sludge discharge port; a magnesium electrode is arranged in the anode chamber, and an anode chamber water inlet is also arranged on the anode chamber; the electrolyte in the anode chamber is sodium chloride solution.
Preferably, the cation exchange membrane is arranged opposite to the air cathode and the magnesium electrode, the cathode chamber water inlet and the cathode chamber water outlet are respectively arranged on two sides of the cation exchange membrane and two sides of the air cathode, and the cathode chamber water inlet is lower than the cathode chamber water outlet.
Preferably, the sludge discharge port at the bottom of the product collecting hopper comprises a product discharge pipe, a closed flange is arranged on the product discharge pipe, and a water stop clamping plate is arranged on the closed flange.
Preferably, the wastewater circulating system comprises an anaerobic digestion solution inlet, a water inlet pipe, a circulating pump, a connecting pipe, a liquid storage tank, a water outlet pipe and an anaerobic digestion solution outlet, wherein the anaerobic digestion solution inlet is connected with the water outlet of the cathode chamber, and the anaerobic digestion solution outlet is connected with the water inlet of the cathode chamber; the anaerobic digestion liquid outlet is connected with the liquid storage tank through a water inlet pipe, the liquid level in the liquid storage tank is higher than the level of the water inlet of the cathode chamber, the water outlet of the circulating pump is connected with the liquid storage tank through a connecting pipe, and the water inlet of the circulating pump is connected with the anaerobic digestion liquid inlet.
Preferably, the top of the anode chamber is provided with a clamping groove for the magnesium electrode to enter and exit.
Preferably, titanium wires are connected to the magnesium electrode and the air cathode, the titanium wires connected to the magnesium electrode extend from the clamping grooves to the outside of the anode chamber, and the titanium wires connected to the air cathode extend to the outside of the cathode chamber.
Preferably, the water inlet of the anode chamber is positioned at the upper part of the anode chamber.
Preferably, each 3.1-4.2cm3The anode chambers are correspondingly configured to be 1-1.3cm2The magnesium electrode of (1); every 2-2.5cm3The cathode chamber is correspondingly arranged by 1-1.25cm22-2.5cm per cathode3The cathode chamber is correspondingly arranged by 1-1.25cm2The cation exchange membrane of (1).
The invention also provides a method for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources, which is carried out by adopting the device for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources by continuously operating the magnesium-air battery, and comprises the following processes:
conveying anaerobic digestion wastewater containing phosphate and ammonium radicals from a water inlet of the cathode chamber to the cathode chamber through a wastewater circulating system to serve as catholyte;
adding sodium chloride solution into the anode chamber from a water inlet of the anode chamber;
electrically connecting two poles of an electric load with a magnesium electrode and an air cathode respectively, wherein the magnesium electrode loses electrons to generate soluble divalent magnesium, soluble divalent magnesium ions enter cathode liquid through a cation exchange membrane and react with ammonium ions and phosphate ions in the cathode liquid to generate magnesium ammonium phosphate precipitate, namely struvite, and the generated struvite is collected and discharged through a product collecting hopper;
electrons lost by the magnesium electrode are transmitted to the air cathode through a circuit; oxygen accepts electrons at the air cathode to form OH-Providing a good pH environment for the generation of struvite; the cation exchange membrane separates the anode chamber from the cathode chamber, and the anode chamber and the cathode chamber maintain charge balance through cation exchange.
Preferably, the concentration of ammonia nitrogen in the anaerobic digestion wastewater is 3420-8118mg/L, the concentration of phosphate is 95-9500mg/, and the concentration of the L sodium chloride solution is 0.01-0.1 mol/L.
The invention has the following beneficial effects:
the device for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources by continuously operating the magnesium-air battery utilizes the zero-valent magnesium with extremely strong reducibility as the anode, so that the reaction rate is higher(ii) a Anaerobic digestion wastewater containing ammonium radicals and phosphate is used as catholyte, the magnesium anode loses electrons, and generated magnesium ions pass through a cation exchange membrane to react with the ammonium radicals and the phosphate in the catholyte to generate struvite, namely a high-quality fertilizer, so that the resource utilization of the wastewater is realized; meanwhile, when the magnesium electrode and the air electrode are used, the magnesium electrode and the air electrode are connected with a power consumption load or an electric energy recovery device, and the purpose of generating electric energy can be achieved; the wastewater circulating system enables the concentration of ammonium radicals and phosphate in the cathode chamber to be maintained at a high level, and ensures the reaction efficiency and stable power generation capacity. Because the anode chamber adopts a neutral sodium chloride solution as an electrolyte solution, magnesium ions generated by electron loss of the magnesium anode are not easy to deposit on the surface of the magnesium anode to form a passivation layer to prevent the reaction from continuing, thereby ensuring the continuous and efficient reaction, and the magnesium ions can reach the cathode through a cation exchange membrane and react with ammonium radicals and phosphate in catholyte to generate struvite; the electrons lost by the magnesium electrode are transmitted to the air cathode through the lead, and the oxygen receives the electrons on the air cathode to generate OH-And a good pH environment is provided for the generation of struvite, so that the magnesium-air battery does not need to add extra alkali to control the pH, thereby reducing the operation cost.
The method for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources can treat wastewater containing ammonium radicals and phosphate by utilizing zero-valent magnesium under the condition of not introducing other impurity ions to obtain struvite, realizes nitrogen and phosphorus removal of the wastewater and recovery of electric energy, and has strong zero-valent magnesium reducibility, so that the reaction speed is high, the anode is not easy to passivate by a cation exchange membrane in a reaction device, the pH of catholyte is suitable for the generation of the struvite, and the continuous, efficient and low-cost operation of the reaction is ensured.
Drawings
FIG. 1 is an overall view of a magnesium-air battery of the present invention continuously operating an apparatus for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources;
FIG. 2 is an overall view of a cathode chamber and an anode chamber of the present invention;
FIG. 3 is an overall view of an anode chamber of the present invention;
FIG. 4 is a sectional view of the cathode chamber and anode chamber integrated structure of the present invention;
fig. 5 is a plan view of an integrated structure of a cathode chamber and an anode chamber according to the present invention.
In the figure: a-cathode chamber, B-anode chamber, 1-1-anaerobic digestion liquid inlet, 1-2-water inlet pipe, 1-3-90 degree elbow, 1-4-circulating pump, 1-5-connecting pipe, 1-6-liquid storage tank, 1-7-water outlet pipe, 1-8-anaerobic digestion liquid outlet, 2-support frame, 3-product discharge pipe, 4-product collecting hopper, 5-air cathode, 6-electric signal collecting system, 7-electric load, 8-magnesium electrode, 9-shell fixing screw, 10-sealing flange, 11-titanium wire, 12-connecting bolt, 13-anode chamber water inlet, 14-clamping groove, 15-wire hole, 16-cation exchange membrane, 16-anion exchange membrane, 17-a water stop splint, 18-screws, 19-screw holes, 20-sealing rings, 22-an external lead, 23-a cathode chamber water inlet and 24-a cathode chamber water outlet.
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 to 5, the device for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources by continuously operating a magnesium-air battery comprises a cathode chamber a and an anode chamber B, wherein a cation exchange membrane 16 is arranged in a channel between the cathode chamber a and the anode chamber B and is hermetically connected with the cathode chamber a through a sealing ring 20, the cathode chamber a is provided with a cathode chamber water outlet 24, an air cathode 5, a cathode chamber water inlet 23 and a product collecting hopper 4 from top to bottom, the cathode chamber water outlet 24 is connected with the cathode chamber water inlet 23 through a wastewater circulating system, the air cathode 5 is connected with a titanium wire 11, the titanium wire 11 extends to the outside of the cathode chamber a, and the bottom of the cathode chamber a is provided with the product collecting hopper 4; the anode chamber B is provided with an anode chamber water inlet 13, a clamping groove 14 and a magnesium electrode 8, the anode chamber water inlet 13 is positioned at the center of the top of the anode chamber B, and the anode chamber water inlet also serves as an exhaust hole in the reaction; the clamping groove 14 is located on one side of the top of the anode chamber B, the clamping groove 14 is opposite to the air cathode 5 of the cathode chamber A, the magnesium electrode 8 is lowered from the clamping groove 14 to the inner cavity of the anode chamber B, the titanium wire 11 is connected onto the magnesium electrode 8, the titanium wire 11 extends to the outside of the anode chamber B, and the titanium wire outside the cathode chamber A can be connected with the electric load 7 through the external lead 22.
As a preferred embodiment of the present invention, as shown in fig. 2, the volume ratio of the cathode chamber a to the anode chamber B is 1:1, in the cathode chamber A, the distance from the cathode chamber water outlet 24 to the top of the cathode chamber A is 1/4 of the total height of the cathode chamber A, the distance from the cathode chamber water inlet 23 to the bottom of the cathode chamber A is 1/4 of the total height of the cathode chamber A, the ratio of the inner diameters of the cathode chamber water outlet 24 and the cathode chamber water inlet 23 is 1:1, in the anode chamber B, the ratio of the inner diameters of the anode chamber water inlet 13 and the cathode chamber water inlet 23 is 1:1, the clamping groove 14 is square, the distance from the clamping groove 14 to the side surface (the left side shown in figure 2) of the anode chamber B is 1/10 of the total length of the anode chamber, the width of the clamping groove 14 is 0.3mm-0.5mm, the magnesium electrode 8 is provided with a wire hole 15, the distance from the wire hole 15 to the upper end of the magnesium electrode 8 is 1/10 of the total height of the magnesium electrode 8, and the ratio of the diameter of the wire hole 15 to the diameter of the titanium wire 11 is 1: 1.
As a preferred embodiment of the present invention, as shown in FIG. 3, after the titanium wire 11 is passed through the wire hole 15 to fix the magnesium electrode 8, the magnesium electrode 8 is put into the anode chamber B from the neck 14, and when the magnesium electrode 8 is replaced, the titanium wire 11 is pulled to pull out the original magnesium electrode 8 for replacement.
As a preferred embodiment of the invention, as shown in FIG. 1, FIG. 2 and FIG. 4, a product collecting hopper 4 is arranged at the bottom of the cathode chamber A, the product collecting hopper 4 is of a chamfered table structure, the inclination angle of the product collecting hopper 4 is 58-62 degrees, a product discharge pipe 3 is connected at the lower end, a water-stop splint 17 is fixed on the product discharge pipe 3, and the water-stop splint 17 is opened every 1-4 days to collect the products of nitrogen and phosphorus removal.
As a preferred embodiment of the invention, as shown in figure 1, the wastewater circulating system comprises an anaerobic digestion solution inlet 1-1, a water inlet pipe 1-2, a 90-degree elbow 1-3, a circulating pump 1-4, a connecting pipe 1-5, a liquid storage tank 1-6, a water outlet pipe 1-7 and an anaerobic digestion solution outlet 1-8, wherein the anaerobic digestion solution inlet 1-1 is arranged at the upper part of one side of a cathode chamber A and is connected with a water outlet 24 of the cathode chamber, and the liquid level in the cathode chamber A is higher than the water outlet 24 of the cathode chamber; anaerobic digestion solution outlets 1-8 are arranged at the lower part of the other side of the cathode chamber A and are connected with a cathode chamber water inlet 23; the anaerobic digestion liquid inlet 1-1 is connected with the liquid storage tank 1-6 through the water inlet pipe 1-7, the connection point is positioned below the liquid level of the liquid storage tank 1-6, the level height of the liquid level of the liquid storage tank 1-6 is higher than the level height of the water inlet 23 of the cathode chamber, so that the wastewater in the liquid storage tank 1-6 can flow into the cathode chamber A under the action of gravity, the water outlet of the circulating pump 1-4 is connected with the liquid storage tank 1-6 through the connecting pipe 1-5, and the water inlet of the circulating pump 1-4 is connected with the anaerobic digestion liquid outlet 1-8 through the water inlet pipe 1-2.
As a preferred embodiment of the present invention, as shown in FIG. 1, the ratio of the volume of the reservoir 1-6 to the total volume of the cathode chamber A and the anode chamber B is 15: 26.
As a preferred embodiment of the present invention, as shown in FIG. 1 and FIG. 2, anaerobic digestion wastewater with ammonia nitrogen concentration of 3420-8118mg/L and phosphate concentration of 95-9500mg/L is fed into the cathode chamber A, and 0.01-0.1mol/L sodium chloride solution is used as electrolyte in the anode chamber B.
As a preferred embodiment of the present invention, as shown in FIGS. 1 and 2, each 3.1 to 4.2cm3The cathode chamber A is correspondingly configured to be 1-1.3cm2The magnesium electrode 8; every 2-2.5cm3The cathode chamber A is correspondingly configured to be 1-1.25cm22-2.5cm per cathode (c)3The cathode chamber A is correspondingly configured to be 1-1.25cm2The cation exchange membrane 16.
As a preferred embodiment of the present invention, as shown in fig. 1 and fig. 2, the cathode chamber a and the anode chamber B are separated by a plexiglass plate, the plexiglass plate is provided with an opening, the cation exchange membrane 16 is fixed at the opening of the plexiglass plate by a sealing ring 20, the cavity of the cathode chamber a is hermetically connected with the plexiglass plate by the sealing ring 20, and the plexiglass plate is hermetically connected with the cathode chamber a by the sealing ring 20. 4 connecting bolts 12 sequentially penetrate through the organic glass cover plate, the anode chamber B, the hollow organic glass plate, the cathode chamber A and the organic glass cover plate from left to right, are screwed and fixed at two ends of the connecting bolts 12 by using shell fixing screws 9, are connected into an integral structure and are placed on the support frame.
In the device for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources by continuously operating the magnesium-air battery, the cathode and the anode respectively adopt the magnesium electrode and the air electrode, the anaerobic digestion wastewater is added into the cathode chamber, and the anodeAdding sodium chloride solution as electrolyte into the chamber; the negative and positive chambers are separated by a cation exchange membrane, and the negative and positive electrodes are connected by an external lead to form a primary battery system. The magnesium anode loses electrons due to the potential difference between the magnesium anode and the air cathode, the electrons reach the air cathode through an external lead, oxygen in the air reaches the catalyst layer through the collection of the gas collecting layer, and reacts with the electrons received by the cathode to generate OH under the action of the Pt/C catalyst-The device provides a good pH condition for denitrification and dephosphorization of anaerobic digestion wastewater, and can generate 1.3V open-circuit voltage in an external circuit; magnesium ions generated by electron loss of the magnesium anode pass through the cation exchange membrane to reach the cathode to react with phosphate and ammonium radicals in the catholyte to generate struvite (MgNH)4PO4·6H2O), an open circuit voltage of 1.3V may be generated in the external circuit. The device realizes nitrogen and phosphorus removal of wastewater by using magnesium ions generated in situ by the magnesium electrode on the premise of not introducing other impurity ions, and simultaneously can recover nitrogen and phosphorus resources and electric energy in the wastewater.
Examples
As shown in fig. 1 to 5, the device for treating anaerobic digestion wastewater and recycling nitrogen and phosphorus resources by continuously operating a magnesium-air battery in the embodiment includes a cathode chamber a, an anode chamber B, external connection equipment and a support frame 2, wherein the cathode chamber a and the anode chamber B are hollow cavities, a hollow cavity in which a cation exchange membrane 16 is located is arranged between the cathode chamber a and the anode chamber B, a sealing ring 20 is arranged at the connection part of the cavities and the cavities, screw holes 19 are formed around all the cavities and are connected in series by connecting bolts 12, and shell fixing screws 9 are fixed at two ends of the connecting bolts 12; the cathode chamber A is connected with a wastewater circulating system which comprises an anaerobic digestion solution inlet 1-1, a water inlet pipe 1-2, a 90-degree elbow 1-3, a circulating pump 1-4, a connecting pipe 1-5, a liquid storage tank 1-6, a water outlet pipe 1-7 and an anaerobic digestion solution outlet 1-8; the cathode chamber A and the anode chamber B transfer mass through a cation exchange membrane 16; an anode chamber water inlet 13, a clamping groove 14, a titanium wire 11 and a magnesium anode 8 are arranged on the anode chamber B; the external connecting equipment comprises an electric signal acquisition system 6, an electric load 7, a shell fixing screw 9 and an external lead 22; after the cathode chamber A, the anode chamber B and the external connecting equipment are assembled and connected, the magnesium-air battery main body is arranged on the support frame 2 and fixed.
As shown in fig. 1 and 2, the air electrode 5 is arranged on the right side of the inner cavity of the cathode chamber a, the right side surface of the air electrode 5 is sealed with the organic glass cover plate through a sealing ring, and the titanium wire 11 extends out of the cathode chamber a from the upper side of the air electrode 5 and is connected with the external lead 22; the product collecting hopper 4 is arranged at the bottom of the cathode chamber A, the lower end of the product collecting hopper is connected with the sludge discharge pipe 3, and the middle part of the sludge discharge pipe 3 is provided with a closed flange 10 for fixing a water stop splint 17; the wastewater circulating system is connected with a cathode chamber water inlet 23 and a cathode chamber water outlet 24 to realize wastewater circulation, the cathode chamber water outlet 24 is connected with an anaerobic digestion liquid inlet 1-1, the anaerobic digestion liquid inlet 1-1 is connected with a circulating pump 1-4 through a water inlet pipe 1-2 and a 90-degree elbow 1-3, the circulating pump 1-4 is connected with a liquid storage tank 1-6 through a connecting pipe 1-5, and the liquid storage tank is connected with an anode chamber water inlet 23 through a water outlet pipe 1-7.
As shown in fig. 1 to 3, the magnesium electrode 8 is arranged on the left side of the inner cavity of the anode chamber B, the left side surface of the anode chamber B is connected with the organic glass cover plate through a sealing ring to realize sealing, the anode chamber water inlet 13 and the clamping groove 14 are arranged on the top of the anode chamber B, the other end of the titanium wire 11 connected with the external lead 22 penetrates through the wire hole 15 to be connected with the magnesium electrode 8, and the magnesium electrode 8 is placed into the anode chamber B from the clamping groove 14.
As shown in fig. 2 and fig. 3, the cation exchange membrane 16 is fixed in the hollow organic glass plate by a sealing ring 20, the cavity of the cathode chamber a is connected with the hollow organic glass plate in a sealing manner by the sealing ring 20, and the hollow organic glass plate is connected with the cathode chamber a in a sealing manner by the sealing ring 20. 4 connecting bolts 12 sequentially penetrate through the organic glass cover plate, the anode chamber B, the hollow organic glass plate, the cathode chamber A and the organic glass cover plate from left to right, are screwed and fixed at two ends of the connecting bolts 12 by using shell fixing screws 9, are connected into an integral structure and are placed on the support frame.
The sizes and proportions of the components can be set according to actual conditions. In this embodiment, the cathode chamber a and the anode chamber B have the same specification, the same volume, and the volume ratio of 1: 1. The cathode chamber A adopts anaerobic digestion wastewater with ammonia nitrogen concentration of 3420-The ratio of the inner diameters of the water inlet 24 and the cathode chamber water inlet 23 is 1: 1; the bottom of the cathode chamber A is provided with a product collecting hopper 4, the product collecting hopper 4 is of a chamfered table structure, the inclination angle of the product collecting hopper 4 is 50-60 degrees, the lower end of the product collecting hopper is connected with a product discharge pipe 3, a water stop clamping plate 17 is fixed on the product discharge pipe 3, and the water stop clamping plate 17 is opened every 4-6 days to collect the denitrification and dephosphorization products. 0.01-0.1mol/L sodium chloride solution can be added into the anode chamber B to serve as electrolyte, the ratio of the inner diameters of a water inlet 13 of the anode chamber to a water inlet 23 of the cathode chamber is 1:1, the clamping groove 14 is square, the distance from the side face of the cathode chamber is 1/10 of the total length of the anode chamber, the width of the clamping groove 14 is 0.5mm, the magnesium electrode 8 is embedded in the clamping groove, a wire hole 15 is formed in the magnesium electrode 8, the distance from the wire hole 15 to the upper end of the magnesium electrode 8 is 1/10 of the total length of the magnesium electrode 8, and the ratio of the diameter of the wire hole 15 to the diameter of the titanium wire is 1: 1. 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. In the wastewater circulating system, the volume ratio of the liquid storage tanks 1-6 to the magnesium-air battery I is 4: 1. The magnesium electrode 8 is a rectangular magnesium sheet which is completely immersed in the electrolyte, and the ratio of the surface area to the volume of the anode chamber B is 1cm2:3.1cm3(ii) a The air electrode 5 is a rectangular thin sheet formed by pressing a carbon-based layer, a diffusion layer and a catalytic layer in combination, is completely immersed in the anaerobic digestion wastewater, and has a ratio of the surface area to the volume of the cathode chamber A of 1cm2：2cm3(ii) a The cation exchange membrane 16 is a rectangular membrane completely immersed in the solution and has a ratio of surface area to volume of the cathode compartment A of 1cm2：2cm3. Through tests, the dimensional proportion and the parameters can well fulfill the test aim of the invention.
The device for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources by utilizing the continuous operation of the magnesium-air battery can be made of organic glass, and the working process is as follows: anaerobic digestion wastewater enters the cathode chamber A from a liquid storage tank 1-6 in the wastewater circulating system through a water outlet pipe 1-7, and the continuous treatment of the wastewater is realized through a circulating pipe pump 1-4. Sodium chloride solution enters the anode chamber B from the water inlet 13 of the anode chamber to be used as anolyte; the magnesium electrode 8 in the anode chamber loses electrons to generate soluble divalent magnesium, and the magnesium ions pass through the cation exchange membrane 16 to enter anolyte and react with ammonium radicals and phosphate radical ions in catholyte to generate birdsPrecipitation of fecalite (MgNH)4PO4·6H2O); struvite is precipitated into a product collecting hopper 4 and periodically discharged through a sludge discharge pipe 3. Electrons lost by the magnesium electrode 8 of the anode chamber are transmitted to the air electrode 5 of the cathode chamber A through the external lead 22 to be combined with oxygen in the air to generate OH-And a good pH condition is provided for the generation of struvite, and meanwhile, current is formed in an external circuit, and data acquisition is carried out by an electric signal collection system 6. The cation exchange membrane 16 separates the anode chamber from the cathode chamber, and the charge balance between the anode chamber and the cathode chamber is maintained by exchanging cations with the cation 16.
The invention has the following characteristics: 1) the zero-valent magnesium has strong reducibility, so that the nitrogen and phosphorus removal rate of the wastewater is high, and the reaction period is short; 2) the anaerobic digestion wastewater can be efficiently treated, and nitrogen and phosphorus resources can be recovered in the form of struvite; 3) continuously operating to maintain the concentration of pollutants at a higher level, so that the nitrogen and phosphorus removal rate of the wastewater is maintained at a higher level; 4) without additional alkali, oxygen of the air cathode is used for generating OH by electrons-Providing a good pH condition for the generation of struvite; 5) the product is generated in the cathode chamber, and the high-concentration sodium chloride solution in the anode chamber avoids the influence of the passivation of the magnesium electrode on the reaction efficiency; 6) the magnesium electrode is convenient to replace.
Claims (10)
1. A magnesium-air battery continuously operates to treat anaerobic digestion wastewater and recover nitrogen and phosphorus resources, and is characterized by comprising a cathode chamber (A), an anode chamber (B), a product collecting hopper (4) and a wastewater circulating system, wherein a communicated passage is arranged between the cathode chamber (A) and the anode chamber (B), and a cation exchange membrane (16) is arranged in the passage; an air cathode (5) is arranged in the inner cavity of the cathode chamber (A), a cathode chamber water inlet (23) and a cathode chamber water outlet (24) are formed in the cathode chamber (A), and the cathode chamber water inlet (23) and the cathode chamber water outlet (24) are connected with a wastewater circulating system; the product collecting hopper (4) is arranged at the bottom of the cathode chamber (A), and a sludge discharge port is formed at the bottom of the product collecting hopper (4); a magnesium electrode (8) is arranged in the anode chamber (B), and an anode chamber water inlet (13) is also arranged on the anode chamber (B); the electrolyte in the anode chamber (B) is a sodium chloride solution.
2. The apparatus for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources in continuous operation of a magnesium-air battery as claimed in claim 1, wherein a cation exchange membrane (16) is disposed opposite to both the air cathode (5) and the magnesium electrode (8), a cathode chamber water inlet (23) and a cathode chamber water outlet (24) are respectively disposed at both sides of the cation exchange membrane (16) and both sides of the air cathode (5), and the cathode chamber water inlet (23) is lower than the cathode chamber water outlet (24).
3. The device for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources by continuously operating the magnesium-air battery as claimed in claim 1, wherein the sludge discharge port at the bottom of the product collecting hopper (4) comprises a product discharge pipe (3), a sealing flange (10) is arranged on the product discharge pipe (3), and a water stop clamping plate (17) is arranged on the sealing flange (10).
4. The magnesium-air battery continuously operated apparatus for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources according to claim 1, wherein the wastewater circulating system comprises an anaerobic digestion solution inlet (1-1), a water inlet pipe (1-2), a circulating pump (1-4), a connecting pipe (1-5), a liquid storage tank (1-6), a water outlet pipe (1-7) and an anaerobic digestion solution outlet (1-8), the anaerobic digestion solution inlet (1-1) is connected with a cathode chamber water outlet (24), and the anaerobic digestion solution outlet (1-8) is connected with a cathode chamber water inlet (23); an anaerobic digestion liquid outlet (1-8) is connected with a liquid storage tank (1-6) through a water inlet pipe (1-7), the liquid level in the liquid storage tank (1-6) is higher than the level of a water inlet (23) of a cathode chamber, a water outlet of a circulating pump (1-4) is connected with the liquid storage tank (1-6) through a connecting pipe (1-5), and a water inlet of the circulating pump (1-4) is connected with an anaerobic digestion liquid inlet (1-1).
5. The device for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources by continuous operation of the magnesium-air battery as claimed in claim 1, wherein the top of the anode chamber (B) is provided with a clamping groove (14) for the magnesium electrode (8) to enter and exit.
6. The device for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources by continuously operating the magnesium-air battery according to claim 5, wherein titanium wires (11) are connected to the magnesium electrode (8) and the air cathode (5), the titanium wires (11) connected to the magnesium electrode (8) extend from the clamping groove (14) to the outside of the anode chamber (B), and the titanium wires (11) connected to the air cathode (5) extend to the outside of the cathode chamber (A).
7. The apparatus for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources with continuous operation of magnesium-air battery as claimed in claim 1, wherein the anode chamber water inlet (13) is located at the upper part of the anode chamber (B).
8. The apparatus for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources by continuous operation of magnesium-air battery as claimed in claim 1, wherein the concentration of magnesium in the magnesium-air battery is 3.1-4.2cm3The anode chamber (B) is correspondingly configured to be 1-1.3cm2The magnesium electrode (8); every 2-2.5cm3The cathode chamber (A) is correspondingly configured to be 1-1.25cm22-2.5cm per each air cathode (5)3The cathode chamber (A) is correspondingly configured to be 1-1.25cm2The cation exchange membrane (16).
9. A method for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources, which is carried out by using the magnesium-air battery of any one of claims 1 to 8 to continuously operate a device for treating anaerobic digestion wastewater and recovering nitrogen and phosphorus resources, and comprises the following processes:
anaerobic digestion wastewater containing phosphate and ammonium radicals is conveyed to the cathode chamber (A) from a cathode chamber water inlet (23) through a wastewater circulating system to be used as catholyte;
adding sodium chloride solution into the anode chamber (B) from a water inlet (13) of the anode chamber;
the two poles of an electric load (7) are respectively electrically connected with a magnesium electrode (8) and an air cathode (5), the magnesium electrode (8) loses electrons to generate soluble divalent magnesium, soluble divalent magnesium ions enter cathode liquid through a cation exchange membrane (16) and react with ammonium ions and phosphate ions in the cathode liquid to generate magnesium ammonium phosphate precipitate, and the generated magnesium ammonium phosphate precipitate is collected and discharged through a product collecting hopper (4);
electricity lost by the magnesium electrode (8)The sub-circuit is transmitted to the air cathode (5); oxygen accepts electrons at the air cathode (5) to form OH-。
10. The method as claimed in claim 9, wherein the concentration of ammonia nitrogen in the anaerobic digestion wastewater is 3420-8118mg/L, the concentration of phosphate is 95-9500mg/L, and the concentration of sodium chloride solution is 0.01-0.1 mol/L.
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| CN116487775A (en) * | 2023-05-09 | 2023-07-25 | 燕山大学 | Preparation method and application of rechargeable magnesium-nitrogen battery |
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