CN220182896U - Electrochemical recovery device for ammonia nitrogen wastewater - Google Patents
Electrochemical recovery device for ammonia nitrogen wastewater Download PDFInfo
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- CN220182896U CN220182896U CN202320593797.5U CN202320593797U CN220182896U CN 220182896 U CN220182896 U CN 220182896U CN 202320593797 U CN202320593797 U CN 202320593797U CN 220182896 U CN220182896 U CN 220182896U
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- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
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Abstract
The utility model provides an electrochemical recovery device for ammonia nitrogen wastewater, which comprises: the electrochemical ammonia recovery tank comprises an anode chamber, a cathode chamber and an ammonia recovery chamber which are adjacent in sequence; the anode chamber is connected with a first feed pump, and the first feed pump pumps the anode into the anode chamber; the cathode chamber is connected with a second feed pump, and the second feed pump pumps ammonia nitrogen wastewater into the cathode chamber; the ammonia recovery chamber is connected with a third feed pump, and the third feed pump pumps the absorption liquid into the ammonia recovery chamber; the anode chamber comprises an anode electrode which is connected with the positive electrode of the power supply; an anion exchange membrane is arranged between the anode chamber and the cathode chamber; and a conductive hydrophobic film is arranged between the cathode chamber and the ammonia recovery chamber and is connected with the negative electrode of the power supply. The utility model can realize in-situ and high-efficiency ammonia nitrogen separation and recovery without adding chemical agents.
Description
Technical Field
The utility model belongs to the field of ammonia nitrogen wastewater recovery, and particularly relates to an electrochemical recovery device for ammonia nitrogen wastewater.
Background
Ammonia (NH) 4 + /NH 3 The method comprises the steps of carrying out a first treatment on the surface of the pka=9.25) is an essential nutrient element for agricultural production and maintenance of functions of land and aquatic ecosystems, is also an important inorganic chemical raw material, and is widely used in the fields of chemical industry, light industry, pharmacy, synthetic fibers, and the like. Meanwhile, because ammonia has high volume energy density relative to hydrogen, the ammonia is used as a high-heat-value carbon-free liquid fuel and a hydrogen energy carrier convenient to transport, and provides a new choice for solving the problems of environmental pollution and energy shortage. The large-scale industrial ammonia synthesis process adopts an energy-intensive Haber-Bosch method, and the production process is accompanied by a large amount of greenhouse gas emission and energy consumption, accounting for 2% of global energy supply and artificial CO 2 The emission amount is 1.2%, and only about 42-47% of nitrogen can be directly utilized in the use process of the nitrogen in the global scope, and the rest of nitrogen enters the environment and finally enters the water body in the form of ammonia nitrogen and nitrate nitrogen, so that the problems of environmental pollution such as water quality deterioration, water body eutrophication aggravation and the like are caused.
The traditional biological denitrification process is whether the nitrification/denitrification process or the nitrosation-anaerobic ammoxidation process currently in hot spot research, and finally converts the nitrosation/denitrification process into N 2 So as to simply realize denitrification of sewage. Consider (i) the Haber Bosch process from elemental nitrogen (N) 2 ) The energy requirements of ammonium, (ii) the electricity required for biological ammonium to remove oxygen demand, and (iii) the energy consumed in the denitrification process, it is apparent that one key feature of achieving overall low energy consumption in wastewater treatment is the realization of energy-efficient recovery of ammonium from the main stream.
The technologies currently available for ammonia recovery are chemical precipitation, stripping/stripping, membrane separation technologies, and the like. Although each of these methods is characterized, there are certain limitations:
chemical precipitation is carried out by adding Mg 2+ 、PO 4 3- (or HPO) 4 2- ) With NH in wastewater 4 + Chemical reaction is carried out to generate double salt NH 4 MgPO 4· H 2 O, NH of the process 4 ：Mg：PO 4 =1: 1:1, the proportion is difficult to achieve in the actual wastewater, so that the consumption of chemical agents is increased if the complete removal of the ammonium is to be achieved in the actual process.
The stripping/stripping method separates ammonia nitrogen in the wastewater in an ammonia mode by adding alkali, then absorbs and converts the ammonia nitrogen into ammonium sulfate by sulfuric acid, and further uses the ammonium sulfate as a fertilizer production raw material, or condenses ammonia obtained after ammonia evaporation by water vapor to form ammonia water so as to realize recycling of the ammonia nitrogen in the wastewater. However, the purity of the recovered ammonium sulfate and ammonia water is not high due to the complex components in the wastewater, so that the alkaline cost of ammonia stripping or ammonia distillation to raise the pH of the wastewater to 10-11 cannot be offset, the denitrification cost of the wastewater is high finally, and the recycling of the ammonia nitrogen in the wastewater cannot be realized.
Membrane separation technology has also received a great deal of attention in improving the separation and purification of wastewater components, especially the application of hydrophobic membranes in the separation of gases and volatile organics, but in order to improve recovery efficiency, alkali still needs to be added to maintain the pH of the solution and provide the driving force for membrane separation.
The electrochemical technology can enter the field of view of researchers by self electrochemical reaction and taking electrons as reducing agents, neither introducing any impurities nor having adverse effect on the environment, and OH is generated by regulating the electrochemical reaction - The method meets the alkali amount required by ammonia recovery, combines membrane recovery with electrochemical reaction, fully plays the technical advantages of the membrane recovery and the electrochemical reaction, and improves the ammonia recovery effect. However, in these separate electrochemical and membrane combinations, NH 3 /OH - The process of generating and diffusing or migrating from the cathode surface into the bulk solution and then separating and recovering the membrane is considered as a main limiting process affecting the ammonia recovery rate, prolongs the ammonia recovery path and causes cathode potential loss.
Disclosure of Invention
In order to solve the problem of lower ammonia recovery rate in the existing ammonia nitrogen wastewater treatment process, the embodiment of the utility model provides an electrochemical recovery device for ammonia nitrogen wastewater, which can realize in-situ and efficient ammonia nitrogen separation and recovery without adding chemical agents.
The embodiment of the utility model provides an electrochemical recovery device for ammonia nitrogen wastewater, which comprises the following components: the electrochemical ammonia recovery tank comprises an anode chamber, a cathode chamber and an ammonia recovery chamber which are adjacent in sequence; the anode chamber is connected with a first feed pump, and the first feed pump pumps the anode into the anode chamber; the cathode chamber is connected with a second feed pump, and the second feed pump pumps ammonia nitrogen wastewater into the cathode chamber; the ammonia recovery chamber is connected with a third feed pump, and the third feed pump pumps the absorption liquid into the ammonia recovery chamber; the anode chamber comprises an anode electrode which is connected with the positive electrode of the power supply; an anion exchange membrane is arranged between the anode chamber and the cathode chamber; and a conductive hydrophobic film is arranged between the cathode chamber and the ammonia recovery chamber and is connected with the negative electrode of the power supply.
The conductive hydrophobic membrane comprises a hydrophobic and breathable base membrane and a conductive catalytic layer, and the conductive catalytic layer is positioned on the surface of the hydrophobic and breathable base membrane.
Wherein the hydrophobic and breathable base film is a PP, PVDF or PTFE hydrophobic and breathable film.
The material of the conductive catalytic layer is noble metal or transition metal with hydrogen evolution performance.
Wherein, the ammonia recovery chamber contains ammonia absorption liquid, and the ammonia absorption liquid is deionized water or acid solution.
Wherein, the ammonia recovery room is connected with the vacuum pump, is connected with the ammonia recovery pond behind the vacuum pump.
Wherein the feed pump is a peristaltic pump or a metering pump.
Wherein the anode electrode is a noble metal electrode or a titanium-based iridium ruthenium electrode.
Wherein the cathode chamber is filled with an ammonium ion adsorbing material.
Wherein the ammonium ion adsorption material is zeolite or cation exchange resin.
The electrochemical recovery device for ammonia nitrogen wastewater has the following beneficial effects:
the electrochemical recovery device for ammonia nitrogen wastewater comprises: the electrochemical ammonia recovery tank comprises an anode chamber, a cathode chamber and an ammonia recovery chamber which are adjacent in sequence; the anode chamber is connected with a first feed pump, and the first feed pump pumps the anode into the anode chamber; the cathode chamber is connected with a second feed pump, and the second feed pump pumps ammonia nitrogen wastewater into the cathode chamber; the ammonia recovery chamber is connected with a third feed pump, and the third feed pump pumps the absorption liquid into the ammonia recovery chamber; the anode chamber comprises an anode electrode which is connected with the positive electrode of the power supply; an anion exchange membrane is arranged between the anode chamber and the cathode chamber; and a conductive hydrophobic film is arranged between the cathode chamber and the ammonia recovery chamber and is connected with the negative electrode of the power supply. The utility model can realize in-situ and high-efficiency ammonia nitrogen separation and recovery without adding chemical agents.
Drawings
FIG. 1 is a schematic diagram of an electrochemical recovery device (acid liquor recovery) for ammonia nitrogen wastewater according to an embodiment of the utility model;
FIG. 2 is a schematic diagram of an electrochemical ammonia recovery tank (acid liquor recovery) of the present utility model;
FIG. 3 is a schematic diagram of an electrochemical recovery device (vacuum recovery) for ammonia nitrogen wastewater according to an embodiment of the utility model;
FIG. 4 is a schematic diagram of an electrochemical ammonia recovery cell of the present utility model (vacuum recovery);
FIG. 5 is a schematic diagram of an electrochemical ammonia recovery tank (low concentration ammonia nitrogen enrichment recovery) of the present utility model.
Detailed Description
The utility model is further described below with reference to the drawings and examples.
The electrochemical and membrane combined process can realize the recovery of high-purity ammonia nitrogen, however, the current research finds that NH 3 The process of separating and recovering/OH-from the cathode surface and diffusing or migrating into the bulk solution to the coating is considered to be a major limiting process affecting the rate of ammonia recovery and also causing a loss of cathode potential. The hydrophobic membrane electrode can realize in-situ separation of ammonia and is helpful forThereby improving the recovery rate. The problems of high consumption of chemical agents, low ammonia recovery efficiency and the like can be effectively solved through the design of the electrochemical reactor, and the method has good application prospect.
As shown in fig. 1 to 5, the electrochemical recovery device for ammonia nitrogen wastewater of the present utility model comprises: an electrochemical ammonia recovery tank comprising an anode chamber 10, a cathode chamber 11 and an ammonia recovery chamber 12 which are adjacent in sequence; the anode chamber 10 is connected with a first feed pump 18, and the first feed pump 18 pumps the anode into the anode chamber 10; the cathode chamber 11 is connected with a second feed pump 19, and the second feed pump 19 pumps ammonia nitrogen wastewater (catholyte) into the cathode chamber 11; the ammonia recovery chamber 12 is connected to a third feed pump 20, and the third feed pump 20 pumps the absorption liquid into the ammonia recovery chamber 12. The anode chamber 10 includes an anode electrode 13, the anode electrode 13 being connected to a positive electrode of a power source 17; an anion exchange membrane 14 is arranged between the anode chamber 10 and the cathode chamber 11; a conductive hydrophobic membrane 15 is arranged between the cathode chamber 11 and the ammonia recovery chamber 12, and the conductive hydrophobic membrane 15 is connected with the negative electrode of a power supply 17.
As shown in fig. 1, the first feed pump 18 is connected to a first feed liquid barrel 29, the first feed liquid barrel 29 is filled with anolyte, the first feed pump 18 is further connected to a first valve 25, the first valve 25 is connected to a first flowmeter 26, and the first flowmeter 26 is connected to the anode chamber 10. The second feed pump 19 is connected with a second feed liquid barrel 30, catholyte is arranged in the second feed liquid barrel 30, the second feed pump 19 is also connected with a second valve 23, the second valve 23 is connected with a second flowmeter 24, and the second flowmeter 24 is connected with the cathode chamber 11. The third feed pump 20 is connected with a third feed liquid barrel 31, the third feed liquid barrel 31 is filled with absorption liquid, the third feed pump 20 is also connected with a third valve 27, the third valve 27 is connected with a third flowmeter 28, and the third flowmeter 28 is connected with the ammonia recovery chamber 12. Wherein the feed pump is a peristaltic pump or a metering pump.
As shown in fig. 1-5, the electrochemical ammonia recovery tank is a closed plate-frame membrane assembly, is fastened by bolts and sealed by rubber gaskets, and is divided into an anode chamber 10, a cathode chamber 11 and an ammonia recovery chamber 12. The anode chamber 10 includes an anode electrode 13 and an anolyte, the anode electrode 13 is, for example, a noble metal electrode or a titanium-based iridium ruthenium electrode, and the anode performs an oxygen evolution reaction to generate H + Realizing acid production function and acid concentration; the anolyte may be dilute sulfurAcid or salt solution such as acid, dilute nitric acid, etc. is prepared according to the required product concentration.
The cathode chamber 11 comprises a conductive hydrophobic membrane 15 and a catholyte, wherein the catholyte is high ammonia nitrogen wastewater or concentrated domestic wastewater or industrial high ammonia nitrogen wastewater; an acid-resistant anion exchange membrane is used between the anode compartment 10 and the cathode compartment 11, in principle allowing only anions of the cathode compartment 11 to migrate towards the anode. A hydrophobic and breathable film (membrane electrode) with a conductive function is adopted between the cathode chamber 11 and the ammonia recovery chamber 12, hydrogen evolution reaction occurs on the surface of the membrane electrode, and OH is generated - The ions, which form molecular ammonia with the ammonium in the water, migrate in situ to the recovery chamber 12 under the influence of a chemical potential or pressure differential across the hydrophobic gas permeable membrane.
The conductive hydrophobic membrane 15 is, for example, a homogeneous hydrophobic breathable membrane containing a conductive material, such as a hydrophobic breathable membrane prepared by mixing PTFE or PVDF with a carbon material. The conductive hydrophobic film 15 includes, for example, a composite film of a hydrophobic and breathable base film and a conductive catalytic layer, the hydrophobic and breathable base film may be a PP (polypropylene), PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene) hydrophobic and breathable film, the conductive catalytic layer on the surface of the hydrophobic and breathable base film is a metal material with hydrogen evolution activity, and may be a noble metal (such as platinum Pt, palladium Pd, etc.), a transition metal simple substance (such as copper, nickel, iron, etc.), or a binary or ternary alloy, and is prepared by a coating or electrodeposition method, and has a porous structure.
As shown in fig. 1-2, the ammonia recovery chamber 12 may be a solution recovery system and the ammonia absorption liquid may be deionized water or an acid solution. Fig. 3 is a schematic diagram of an electrochemical ammonia nitrogen wastewater recovery device (vacuum recovery) according to an embodiment of the present utility model, and fig. 3 is different from fig. 1 in that vacuum recovery is adopted, an ammonia recovery chamber 12 is connected with a vacuum pump 21, an ammonia recovery tank 33 is connected behind the vacuum pump 21, a valve 16 and a vacuum gauge 32 are further disposed between the ammonia recovery chamber 12 and the vacuum pump 21, and deionized water or an acid solution is in the ammonia recovery tank 33. As shown in fig. 3-4, the ammonia recovery chamber 12 is formed into a negative pressure vacuum chamber by a vacuum pump 21 to pump ammonia out into an electrochemical ammonia recovery tank 33 for recovery.
As shown in fig. 5, for low concentration ammonia nitrogen wastewater, in order to improve ammonia recovery efficiency, the cathode chamber 11 may be filled with an ammonium ion adsorption material 22. So that the ammonium ions entering the cathode chamber 11 are first rapidly immobilized by the adsorbent material 22, and then the ammonium ions residing in the cathode chamber 11 are desorbed and migrate towards the cathode under the influence of the electric field and are recovered in situ by the conductive hydrophobic membrane 15. The ammonium ion adsorption material can be zeolite, cation exchange resin or self-prepared particle material capable of realizing the ammonia adsorption function.
The electrochemical reaction occurring in the electrochemical recovery device of ammonia nitrogen wastewater of the utility model is as follows:
anode reaction:
H 2 O→2H + (aq) +(1/2)O 2(g) +2e - E 0 ＝1.229 V (1)
cathode reaction:
2H 2 O+2e - →2OH - (aq) +H 2(g) E 0 ＝-0.828 V (2)
NH 3 .H 2 O (aq) →NH 3(g) +H 2 O (4)
in an electrochemical and membrane combined structure, NH 3 /OH - The process of generating and diffusing or migrating from the cathode surface into the bulk solution and then separating and recovering the membrane is considered as a main limiting process affecting the ammonia recovery rate, prolongs the ammonia recovery path and causes cathode potential loss. The utility model utilizes the in-situ pH change of the partial surface of the electrode to reduce OH - /NH 3 Migration loss into the bulk solution increases ammonia recovery efficiency. Electrode surface ammonia recovery prevents OH - /NH 3 Thereby reducing surface pH and overpotential and improving ammonia production. Besides ammonia recovery, negative potential on the membrane electrode can repel negatively charged dirt, reducing membrane contamination. The hydrophobic support of the membrane electrode prevents penetration of other particles, thereby ensuring high purity of ammonia in the recovery solution.
The utility model realizes the following technical effects:
1. the device can realize synchronous conversion from ammonium to gaseous ammonia and high-efficiency recovery in one reactor; 2. aiming at high-concentration ammonia nitrogen wastewater, the concentration of acid can be realized while the recovery of ammonia is realized; 3. aiming at low-concentration ammonia nitrogen wastewater, the enrichment of ammonium radicals and the synchronous recovery of ammonia can be realized; 4. the partial alkaline environment of the conductive hydrophobic membrane can greatly reduce the pH value of the solution main body of the cathode chamber while realizing ammonia recovery; 5. negative potential on the surface of the conductive hydrophobic membrane can repel dirt with negative charge, and membrane pollution is reduced; 6. the hydrophobic support of the membrane electrode prevents penetration of other particles, thereby ensuring high purity of ammonia in the recovery solution.
The above description is only of the preferred embodiments of the present utility model and is not intended to limit the present utility model, but various modifications and variations can be made to the present utility model by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present utility model should be included in the protection scope of the present utility model.
Claims (10)
1. An electrochemical recovery device for ammonia nitrogen wastewater, which is characterized by comprising: the electrochemical ammonia recovery tank comprises an anode chamber, a cathode chamber and an ammonia recovery chamber which are adjacent in sequence; the anode chamber is connected with a first feed pump, and the first feed pump pumps the anode into the anode chamber; the cathode chamber is connected with a second feed pump, and the second feed pump pumps ammonia nitrogen wastewater into the cathode chamber; the ammonia recovery chamber is connected with a third feed pump, and the third feed pump pumps the absorption liquid into the ammonia recovery chamber; the anode chamber comprises an anode electrode which is connected with the positive electrode of the power supply; an anion exchange membrane is arranged between the anode chamber and the cathode chamber; and a conductive hydrophobic film is arranged between the cathode chamber and the ammonia recovery chamber and is connected with the negative electrode of the power supply.
2. The electrochemical recovery device for ammonia nitrogen wastewater according to claim 1, wherein the conductive hydrophobic membrane comprises a hydrophobic and breathable base membrane and a conductive catalytic layer, and the conductive catalytic layer is positioned on the surface of the hydrophobic and breathable base membrane.
3. The electrochemical recovery device of ammonia nitrogen wastewater according to claim 2, wherein the hydrophobic and breathable base membrane is PP, PVDF or PTFE hydrophobic and breathable membrane.
4. The electrochemical recovery device for ammonia nitrogen wastewater according to claim 2, wherein the conductive catalytic layer is made of noble metal or transition metal with hydrogen evolution performance.
5. The electrochemical recovery apparatus for ammonia nitrogen wastewater according to any one of claims 1 to 4, wherein the ammonia recovery chamber contains an ammonia absorbing liquid, and the ammonia absorbing liquid is deionized water or an acid solution.
6. The electrochemical recovery device for ammonia nitrogen wastewater according to any one of claims 1 to 4, wherein the ammonia recovery chamber is connected with a vacuum pump, and an ammonia recovery tank is connected behind the vacuum pump.
7. The electrochemical recovery device for ammonia nitrogen wastewater according to any one of claims 1 to 4, wherein the feed pump is a peristaltic pump or a metering pump.
8. The electrochemical recovery apparatus for ammonia nitrogen wastewater according to any one of claims 1 to 4, wherein the anode electrode is a noble metal electrode or a titanium-based iridium ruthenium electrode.
9. The electrochemical recovery apparatus for ammonia nitrogen wastewater according to any one of claims 1 to 4, wherein the cathode chamber is filled with an ammonium ion adsorption material.
10. The electrochemical recovery device for ammonia nitrogen wastewater according to claim 9, wherein the ammonium ion adsorption material is zeolite or cation exchange resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202320593797.5U CN220182896U (en) | 2023-03-23 | 2023-03-23 | Electrochemical recovery device for ammonia nitrogen wastewater |
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