CN114524493B - Ammonia recovery device and method for electrochemically treating nitrate wastewater - Google Patents
Ammonia recovery device and method for electrochemically treating nitrate wastewater Download PDFInfo
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- CN114524493B CN114524493B CN202210088024.1A CN202210088024A CN114524493B CN 114524493 B CN114524493 B CN 114524493B CN 202210088024 A CN202210088024 A CN 202210088024A CN 114524493 B CN114524493 B CN 114524493B
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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
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/026—Preparation of ammonia from inorganic compounds
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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
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides an ammonia recovery device for electrochemically treating nitrate wastewater, which comprises an electrochemical reactor, wherein an anode chamber and a cathode chamber are arranged in the electrochemical reactor, the anode chamber and the cathode chamber are separated by a proton exchange membrane, and an ammonia recovery chamber is also arranged in the electrochemical reactor; the anode chamber, the cathode chamber and the ammonia recovery chamber are sequentially and adjacently arranged, a counter electrode is arranged in the anode chamber, the cathode chamber and the ammonia recovery chamber are separated by a diaphragm, and the diaphragm is composed of an electrode material and a waterproof breathable material; the ammonia recovery device further comprises an electrolyte storage tank, a nitrate storage tank, an ammonia absorption liquid storage tank and a constant flow pump, wherein the electrolyte storage tank, the nitrate storage tank, the ammonia absorption liquid storage tank and the constant flow pump are used for forming external circulation. The invention can convert high-concentration nitrate into ammonia ions, can directly recover available ammonium salt products, and can directly obtain high-purity resource substances in a clean and environment-friendly manner while purifying high-concentration nitrate wastewater.
Description
Technical Field
The invention relates to the field of recovering ammonia by electrochemically reducing nitrate, in particular to an ammonia recovery device and method for electrochemically treating nitrate wastewater.
Background
Nitrogen is one of the chemical elements necessary to sustain life activities. The nitrogen in the water body mainly exists in two forms of organic nitrogen and inorganic nitrogen. The organic nitrogen is mainly represented by protein, urea, etc., and the inorganic nitrogen includes ammonia Nitrogen (NH) 4 + Or NH 3 ) Nitrate (NO) 3 - ) Nitrite (NO) 2 - ) Nitrogen (N) 2 ) And the like. Nitrogen in the nature migrates and transforms among the environment and various organisms to form nitrogen cycle, but the nitrogen cycle is destroyed because of a large amount of nitrogen-containing wastewater which is not treated or discharged after reaching standards in industrial production, thereby causing nitrogen pollution. Wherein the high concentration of NO 3 - Wastewater is one of the main causes of imbalance in nitrogen cycle. Wastewater generated in the industries of steel smelting, electroplating, chemical fertilizer, nuclear fuel, electronic elements and the like contains high-concentration NO 3 - . NO in waste water from cleaning of metal devices with concentrated nitric acid, e.g. in the nuclear industry 3 - The concentration is up to 50000mg N/L. Therefore, how to effectively treat high concentration NO generated in the industry 3 - Wastewater becomes one of the difficulties in the field of water pollution control.
Ammonia (NH) 3 ) Is an indispensable raw material for manufacturing chemical products such as chemical fertilizers, medicines, dyes and the like, and is convenient to store and combust without discharging carbon dioxide (CO) by virtue of zero carbon, large energy density, high hydrogen content 2 ) The characteristics of the fuel are a potential green energy carrier and fuel. At present, NH 3 The synthesis mainly depends on the Haber-Bosch (Haber-Bosch) process, the total annual production of the whole world is about 2 hundred million tons, and the synthesis is the second largest chemical and commercial product in the world. But the method has harsh reaction conditions (high temperature and high pressure of 300-500 ℃, 200-300 atm), high energy consumption (1-2 percent of the global energy consumption), and large amount of CO emission 2 、CH 4 And the like. Synthesizing unit product NH according to chemical industry standard HG/T4487-2012 of the people's republic of China 3 Carbon emission of about 1.5tCO 2 /tNH 3 . Ammonia energy association (Ammonia energy association) preliminary statistics, produced annually worldwideNH 3 The amount of carbon emitted is-1.6% of the total amount of global carbon emissions.
Thus, NO in the nitrate wastewater is removed 3 - Conversion of NH 4 + Further recovering NH 3 Not only can complete the treatment of nitrate wastewater, but also can obtain NH in a clean manner 3 . At present, although there is a related research on the electrochemical reaction of NO 3 - Conversion to NH 4 + However, the existing research is mainly focused on NH 4 + In particular involving NH 3 Moreover, the effect of the existing research on ammonia recovery from high nitrate content wastewater is not ideal.
Therefore, there is a need for an ammonia recycling apparatus and method for electrochemically treating nitrate wastewater, so as to solve or at least alleviate the above-mentioned disadvantages of inconvenience in recycling ammonia and difficulty in treating high-concentration nitrate wastewater.
Disclosure of Invention
The invention mainly aims to provide an ammonia recovery device and method for electrochemically treating nitrate wastewater, and aims to solve the technical problems of inconvenience in ammonia recovery and utilization and difficulty in high-concentration nitrate wastewater treatment.
In order to achieve the aim, the invention provides an ammonia recovery device for electrochemically treating nitrate wastewater, which comprises an electrochemical reactor, wherein an anode chamber and a cathode chamber are arranged in the electrochemical reactor, the anode chamber and the cathode chamber are separated by a proton exchange membrane, and an ammonia recovery chamber is also arranged in the electrochemical reactor;
the anode chamber, the cathode chamber and the ammonia recovery chamber are sequentially and adjacently arranged, a counter electrode is arranged in the anode chamber, the cathode chamber and the ammonia recovery chamber are separated by a diaphragm, and the diaphragm comprises an air electrode;
the ammonia recovery device also comprises an electrolyte storage tank, a nitrate storage tank, an ammonia absorption liquid storage tank and a constant flow pump;
the liquid outlet part of the electrolyte storage tank is communicated with the liquid inlet of the anode chamber through the constant flow pump; the liquid outlet part of the nitrate storage tank is communicated with the liquid inlet of the cathode chamber through the constant flow pump; and the liquid outlet part of the ammonia absorption liquid storage tank is communicated with the liquid inlet of the ammonia recovery chamber through the constant flow pump.
Further, the counter electrode is a dimensionally stable anode comprising one of lead oxide, iridium oxide, ruthenium oxide and a boron doped diamond film electrode.
Further, a reference electrode is arranged in the cathode chamber; the reference electrode comprises one of silver chloride, saturated calomel and standard hydrogen electrodes.
Further, the preparation process of the air electrode comprises the following steps: uniformly coating the mixture of the material with the activity of electrochemically reducing nitrate and acetylene black on the surface of a waterproof breathable film to obtain the air electrode;
wherein the material with activity of electrochemical reduction of nitrate comprises one or more of ilmenite, cobalt phosphide, nano zero-valent iron, cobaltosic oxide, nano zero-valent copper and titanium dioxide.
Further, an anolyte is stored in the electrolyte storage tank and comprises a sodium sulfate solution.
Further, nitrate wastewater is stored in the nitrate storage tank, and the concentration range of nitrate in the nitrate wastewater is 500-50000mg N/L.
Further, an ammonia absorption liquid is stored in the ammonia absorption liquid storage tank, and the ammonia absorption liquid comprises one of a sulfuric acid solution, a hydrochloric acid solution and a carbonic acid solution.
Further, a liquid inlet part of the electrolyte storage tank is communicated with a liquid outlet of the anode chamber; the liquid inlet part of the nitrate storage tank is communicated with the liquid outlet of the cathode chamber; and the liquid inlet part of the ammonia absorption liquid storage tank is communicated with the liquid outlet of the ammonia recovery chamber.
Furthermore, a liquid inlet and a liquid outlet of the anode chamber are arranged oppositely, and the height of the liquid inlet of the anode chamber is lower than that of the liquid outlet;
the liquid inlet and the liquid outlet of the cathode chamber are arranged oppositely, and the liquid inlet of the cathode chamber is lower than the liquid outlet;
the liquid inlet and the liquid outlet of the ammonia recovery chamber are arranged oppositely, and the height of the liquid inlet of the ammonia recovery chamber is lower than that of the liquid outlet.
The invention also provides an ammonia recovery method, which adopts the ammonia recovery device to recover ammonia from nitrate wastewater.
Compared with the prior art, the invention has the following advantages:
the method can convert high-concentration nitrate into an ammonium salt product which can be directly recycled, and can directly obtain high-purity resource substances in a clean and environment-friendly manner while purifying high-concentration nitrate wastewater. Specifically, the method comprises the following steps:
1. the diaphragm is combined with the ammonia absorption chamber, and because the diaphragm is a waterproof breathable film which is conductive and has the performance of electrochemically reducing nitrate into ammonium ions, nitrate can be converted into the ammonium ions under the condition of electrochemical reaction, and the conversion of the ammonium ions into ammonia gas is promoted by virtue of the local rise of pH, so that pressure difference is formed at two sides of the diaphragm, the ammonia gas enters the ammonia recovery chamber from the cathode chamber in the continuous generation process, and then the ammonia gas is converted into an ammonia salt product in the ammonia recovery chamber.
2. The invention combines the external circulation mode with the electrochemical reactor, the constant flow pump pumps the electrolyte, the nitrate wastewater and the ammonia absorption liquid in the storage tank into the corresponding electrolytic cell, and the electrolyte, the nitrate wastewater and the ammonia absorption liquid directly return to the storage tank from the liquid outlet at the upper part, so that the solution can be always in a flowing and uniform state, the stirring link is saved, the equipment occupation is reduced, and the energy is saved. In addition, the nitrate solution in the cathode chamber is always in a constant-current state, similar to a capacitive deionization model, and ammonium ions generated by electrochemical denitrification under the drive of an electric field can directionally move to the surface of the conductive waterproof breathable film, so that ammonia recovery is facilitated; and the ammonia recovery chamber is in a circulating constant-current state, so that ammonia gas entering the ammonia recovery chamber can be continuously absorbed, and the pressure difference between two sides of the diaphragm is ensured to be continuously existed.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without any creative work.
FIG. 1 is a schematic block diagram of an ammonia recovery unit according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of an electrochemical reactor according to an embodiment of the present invention;
FIG. 3 is a schematic view of the structure of an electrochemical reactor according to another embodiment of the present invention (the counter electrode and the reference electrode are not shown);
FIG. 4 is a graph showing the effect of data on the treatment of high-concentration nitrate wastewater in example 2 of the present invention.
Reference numerals: 1. an electrochemical reactor; 2. an anode chamber; 3. a counter electrode; 4. a proton exchange membrane; 5. a cathode chamber; 6. a reference electrode; 7. a diaphragm; 8. an ammonia recovery chamber; 9. an electrolyte storage tank; 10. a nitrate storage tank; 11. an ammonia absorption liquid storage tank; 12. a constant flow pump; 13. a first housing; 14. a first spacer; 15. A second gasket; 16. a second housing; 17. a third gasket; 18. a fourth gasket; 19. a third housing.
The implementation, functional features and advantages of the present invention will be further described with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
It should be noted that all directional indicators (such as upper and lower 8230; etc.) in the embodiments of the present invention are only used for explaining the relative positional relationship between the components in a specific posture (as shown in the figure), the motion situation, etc., and if the specific posture is changed, the directional indicator is correspondingly changed.
In addition, descriptions such as "first", "second", etc. in the present invention are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature.
Moreover, the technical solutions in the embodiments of the present invention may be combined with each other, but it is necessary to be able to be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent, and is not within the protection scope of the present invention.
It should be noted that the prior art is deficient in the treatment of high-concentration nitrates, and meanwhile, the preparation of electrode materials generally used for recovering ammonia by electrochemical reduction of nitrates is complex, the cost is high, and a certain research space is left for industrialization.
To realize the purification of high-concentration nitrate wastewater and simultaneously recover NH 3 Resource, referring to fig. 1-3, the invention provides an ammonia recovery device for electrochemically treating nitrate wastewater, comprising an electrochemical reactor 1, wherein an anode chamber 2 and a cathode chamber 5 are arranged in the electrochemical reactor 1, and the anode chamber 2 and the cathode chamber 5 are separated by a proton exchange membrane 4.
On the basis, in order to realize the recovery of ammonia, an ammonia recovery chamber 8 is also arranged in the electrochemical reactor 1, so as to obtain an ammonium salt product in the ammonia recovery chamber 8.
In order to ensure the electrochemical reaction, the anode chamber 2, the cathode chamber 5 and the ammonia recovery chamber 8 are arranged next to each other in sequence, and a counter electrode 3 is arranged in the anode chamber 2. The cathode chamber 5 and the ammonia recovery chamber 8 are separated by a diaphragm 7, and the diaphragm 7 is an air electrode and mainly comprises an electrode material and a waterproof and breathable material. Certainly, in the process of carrying out electrochemical reaction, the inside of the electrochemical reaction device needs to be isolated from the outside, and meanwhile, an external power supply device needs to be introduced for supplying power, and the research of electrochemically treating high-concentration nitrate wastewater and recovering ammonia is carried out by applying constant voltage or constant current driving through an external power supply device; the power supply device can be an electrochemical workstation, a stabilized voltage power supply, a direct current power supply or a transverse potentiometer.
It should be noted that the counter electrode 3 serves as an anode, and the diaphragm 7, on the basis of serving as a cathode (working electrode), can make ammonia gas smoothly enter the ammonia recovery chamber 8, and during the reaction, the pH at the diaphragm 7 will rise to 10 or even higher, so that ammonium ions converted from nitrate nitrogen will generate a large amount of ammonia gas at the diaphragm 7 (the side close to the cathode chamber 5), so that a pressure difference is formed between the two sides of the diaphragm 7, and ammonia gas is ensured to pass through the diaphragm 7 and enter the ammonia recovery chamber 8.
In addition, in order to improve the efficiency of reaction and recovery with reduced equipment footprint and energy saving, the ammonia recovery apparatus further includes an electrolyte storage tank 9, a nitrate storage tank 10, an ammonia absorption liquid storage tank 11, and a constant flow pump 12; the liquid outlet part of the electrolyte storage tank 9 is communicated with the liquid inlet of the anode chamber 2 through the constant flow pump 12, and the liquid inlet part of the electrolyte storage tank 9 is communicated with the liquid outlet of the anode chamber 2; the liquid outlet part of the nitrate storage tank 10 is communicated with the liquid inlet of the cathode chamber 5 through the constant flow pump 12, and the liquid inlet part of the nitrate storage tank 10 is communicated with the liquid outlet of the cathode chamber 5; the liquid outlet part of the ammonia absorption liquid storage tank 11 is communicated with the liquid inlet of the ammonia recovery chamber 8 through the constant flow pump 12, and the liquid inlet part of the ammonia absorption liquid storage tank 11 is communicated with the liquid outlet of the ammonia recovery chamber 8.
It should be noted that, under the action of the constant flow pump 12, not only can the substances in the anode chamber 2, the cathode chamber 5 and the ammonia recovery chamber 8 realize circulating flow, thereby playing roles of stirring and liquid exchange; moreover, since the substance in the cathode chamber 5 is in the flowing process, the ammonium ions generated in the cathode chamber 5 can easily move to the surface of the diaphragm 7 directionally under the driving of the electric field, and generate ammonia gas under the action of high pH, so as to ensure that the diaphragm 7 has high pressure at one side of the cathode chamber 5, and at the same time, since the ammonia gas entering the ammonia recovery chamber 8 will take part in the circulating flow after being converted into the ammonium salt product, the ammonia gas at one side of the cathode chamber 5 can be ensured to continuously enter the ammonia recovery chamber 8 and be converted into the desired ammonium salt product.
It should be noted that, because the conversion of the ammonium ions into ammonia gas is a reversible reaction, under the above conditions, the ammonia gas continuously enters the ammonia recovery chamber 8, and the conversion efficiency of the ammonium ions into ammonia gas can be further ensured, so that the recovery efficiency and the recovery speed of ammonia are improved, and the formation of the above conditions can be further ensured.
The specific process in the above embodiment is as follows: on the basis of electrochemical reaction, nitrate ions entering the cathode chamber 5 are converted into ammonium ions; the surface of the diaphragm 7 is increased in pH value due to reduction of electrolytic water or nitrate, so that conversion of ammonium ions to ammonia is facilitated; when the ammonium ions begin to convert into ammonia, a pressure difference is formed between two sides of the diaphragm 7, so that the converted ammonia enters the ammonia recovery chamber 8 and is converted into an ammonia salt product by a sulfuric acid solution and other substances circularly flowing in the ammonia recovery chamber 8, and the purification of nitrate wastewater and the acquisition of the ammonia product are realized.
As an illustration of the counter electrode 3, the counter electrode 3 is a dimensionally stable anode comprising one of lead oxide, iridium oxide, ruthenium oxide and a boron doped diamond thin film electrode.
As an explanation of the electrochemical reactor 1, the electrochemical reactor 1 may be a three-electrode system, and a reference electrode 6 may be provided in the cathode chamber 5 when a reaction is performed in the three-electrode system. The reference electrode 6 comprises one of silver chloride, saturated calomel and standard hydrogen electrodes.
As an explanation of the separator 7, the separator 7 may be configured as a waterproof air-permeable film, i.e., an air electrode, which is electrically conductive and has a property of electrochemically reducing nitrate to ammonium ions. The preparation process of the air electrode comprises the following steps: uniformly coating the mixture of the material with the activity of electrochemically reducing nitrate and acetylene black on the surface of a waterproof breathable film to obtain the air electrode; wherein the material with the activity of electrochemically reducing nitrate comprises one or more of ilmenite, cobalt phosphide, nano zero-valent iron, cobaltosic oxide, nano zero-valent copper and titanium dioxide.
Illustratively, the preparation process of the separator 7 may include: and coating a mixture of ilmenite powder and acetylene black on the surface of the polytetrafluoroethylene to obtain the diaphragm 7. Because the diaphragm 7 contains ilmenite, the diaphragm has high stability, corrosion resistance and conductivity, and can purify not only the nitrate wastewater with the first concentration, but also the high-concentration wastewater. For example, nitrate wastewater with a nitrate concentration in the range of 500-50000mg N/L can be purified and an ammonium salt product obtained.
As an explanation of the electrolyte storage tank 9, the nitrate storage tank 10, and the ammonia absorbing liquid storage tank 11, an anolyte solution including a sodium sulfate solution is stored in the electrolyte storage tank 9. Nitrate waste water is stored in the nitrate storage tank 10, and the concentration range of nitrate in the nitrate waste water can be 500-50000mg N/L. The ammonia absorption liquid storage tank 11 stores therein ammonia absorption liquid including one of a sulfuric acid solution, a hydrochloric acid solution, and a carbonic acid solution.
As a preferable mode of the above embodiment, in order to ensure the circulation flow of the liquid, the liquid inlet and the liquid outlet of the anode chamber 2 are arranged oppositely, and the liquid inlet of the anode chamber 2 is lower than the liquid outlet; the liquid inlet and the liquid outlet of the cathode chamber 5 are arranged oppositely, and the liquid inlet of the cathode chamber 5 is lower than the liquid outlet; the liquid inlet and the liquid outlet of the ammonia recovery chamber 8 are arranged oppositely, and the height of the liquid inlet of the ammonia recovery chamber 8 is lower than that of the liquid outlet. Besides ensuring the circulating flow of liquid, the liquid inlet of the cathode chamber 5 is lower than the liquid outlet, and ammonia gas can enter the ammonia recovery device during the movement from bottom to top, so that the recovery efficiency is improved.
The invention also provides an ammonia recovery method, which adopts the ammonia recovery device in any embodiment to recover ammonia from nitrate wastewater.
To facilitate understanding of the above embodiments, the following will be exemplified:
example 1
Referring to fig. 1 to 3, an ammonia recovery apparatus includes an electrolyte storage tank 9, a nitrate storage tank 10, an ammonia absorbing liquid storage tank 11, a constant flow pump 12, and an electrochemical reactor 1.
Electrochemical reactor 1 is including transversely arranging first casing 13, second casing 16 and third casing 19 in proper order, the indent is formed with anode chamber 2 on first casing 13 on horizontal, be formed with the cathode chamber 5 that transversely runs through on the second casing 16, third casing 19 is the indent is formed with ammonia recovery chamber 8 on horizontal, anode chamber 2 with ammonia recovery chamber 8 sets up relatively, be equipped with counter electrode 3 in the anode chamber 2, be equipped with reference electrode 6 in the cathode chamber 5.
A first gasket 14, a proton exchange membrane 4 and a second gasket 15 are sequentially arranged between the first shell 13 and the second shell 16; a third gasket 17, the diaphragm 7 (i.e., an air electrode) and a fourth gasket 18 are sequentially arranged between the second casing 16 and the third casing 19, and a transverse through channel is formed on each of the first gasket 14, the second gasket 15, the third gasket 17 and the fourth gasket 18, so that the electrochemical reaction and the movement of the substance are facilitated.
The first housing 13, the first gasket 14, the second gasket 15, the proton exchange membrane 4, the second housing 16, the third gasket 17, the diaphragm 7, the fourth gasket 18, and the third housing 19 are sealingly connected by fasteners.
Liquid inlets are formed in the lower parts of the anode chamber 2, the cathode chamber 5 and the ammonia recovery chamber 8, and liquid outlets are formed in the upper parts of the anode chamber, the cathode chamber and the ammonia recovery chamber; a liquid inlet of the anode chamber 2 is communicated with the electrolyte storage tank 9 through the constant flow pump 12, and a liquid outlet of the anode chamber 2 is also communicated with the electrolyte storage tank; a liquid inlet of the cathode chamber 5 is communicated with the nitrate storage tank 10 through the constant flow pump 12, and a liquid outlet of the cathode chamber 5 is also communicated with the nitrate storage tank; the liquid inlet of the ammonia recovery chamber 8 is communicated with the ammonia absorption liquid storage tank 11 through the constant flow pump 12, and the liquid outlet of the ammonia recovery chamber 8 is communicated with the ammonia absorption liquid storage tank.
Example 2
An experiment for recovering ammonia by electrochemically treating high-concentration nitrate wastewater was carried out by using the ammonia recovery apparatus in example 1.
Wherein the anolyte is 0.1M sodium sulfate (50 mL); the high-concentration nitrate wastewater adopts simulated nitrate wastewater (50 mL) prepared by ultra-pure water, and the simulated nitrate wastewater contains 0.1M sodium sulfate and 1000mg N/L nitrate; 0.1M sulfuric acid (50 mL) is adopted as ammonia absorption liquid; the shape-stable anode adopts ruthenium dioxide (4 cm multiplied by 4 cm); reference electrode 6 is silver chloride.
The separator 7 (4 cm. Times.4 cm) was prepared by the following procedure: mixing 200mg of ilmenite powder with 25mg of acetylene black to obtain a mixture; dispersing the mixture in a nitrogen-nitrogen dimethyl pyrrolidone solution of 5mL of 10g/L polyvinylidene fluoride to obtain black slurry; and uniformly coating the black slurry on the surface of the polytetrafluoroethylene waterproof and breathable film by using a spraying machine to obtain the diaphragm (namely the air electrode).
The flow rate of the constant flow pump 12 was 120. Mu.L/min, and a constant voltage of-1.9V vs. Ag/AgCl was applied to the membrane using a Wantong electrochemical workstation.
The experimental results are shown in fig. 4, and the removal rate of nitrate, the generation rate of ammonium ions and the recovery rate of ammonia after 10 hours of electrolytic reaction are 91.1%,77.6% and 85.9%, respectively; wherein, the generation rate of ammonium ions refers to: conversion rate of ammonium ions in the degraded nitrate; recovery of ammonia refers to: recovery of ammonia from the converted ammonium ion. Therefore, the ammonia recovery device and method provided by the invention can synchronously realize the dual purposes of treating high-concentration nitrate wastewater and recovering ammonia.
In the above technical solutions, the above are only preferred embodiments of the present invention, and the technical scope of the present invention is not limited thereby, and all the technical concepts of the present invention include the claims of the present invention, which are directly or indirectly applied to other related technical fields by using the equivalent structural changes made in the description and drawings of the present invention.
Claims (9)
1. An ammonia recovery device for electrochemically treating nitrate wastewater comprises an electrochemical reactor, wherein an anode chamber and a cathode chamber are arranged in the electrochemical reactor, and are separated by a proton exchange membrane, and the ammonia recovery device is characterized in that an ammonia recovery chamber is also arranged in the electrochemical reactor;
the anode chamber, the cathode chamber and the ammonia recovery chamber are sequentially and adjacently arranged, a counter electrode is arranged in the anode chamber, the cathode chamber and the ammonia recovery chamber are separated by a diaphragm, and the diaphragm comprises an air electrode;
the preparation process of the air electrode comprises the following steps: uniformly coating the mixture of the material with the activity of electrochemically reducing nitrate and acetylene black on the surface of a waterproof breathable film to obtain the air electrode;
the ammonia recovery device also comprises an electrolyte storage tank, a nitrate wastewater storage tank, an ammonia absorption liquid storage tank and a constant flow pump;
the liquid outlet part of the electrolyte storage tank is communicated with the liquid inlet of the anode chamber through the constant flow pump; the liquid outlet part of the nitrate wastewater storage tank is communicated with the liquid inlet of the cathode chamber through the constant flow pump; the liquid outlet part of the ammonia absorption liquid storage tank is communicated with the liquid inlet of the ammonia recovery chamber through the constant flow pump;
the liquid inlet part of the electrolyte storage tank is communicated with the liquid outlet of the anode chamber; the liquid inlet part of the nitrate wastewater storage tank is communicated with the liquid outlet of the cathode chamber; the liquid inlet portion of ammonia absorption liquid storage jar with the liquid outlet intercommunication setting of ammonia recovery room.
2. The ammonia recovery device of claim 1, wherein the counter electrode is a dimensionally stable anode comprising one of lead oxide, iridium oxide, ruthenium oxide, and boron doped diamond film electrodes.
3. The ammonia recovery device of claim 1, wherein a reference electrode is disposed within the cathode chamber; the reference electrode comprises one of silver chloride, saturated calomel and standard hydrogen electrode.
4. The ammonia recovery unit of claim 1, wherein the material having electrochemical nitrate reduction activity comprises one or more of ilmenite, cobalt phosphide, nano zero-valent iron, tricobalt tetraoxide, nano zero-valent copper, and titania.
5. The ammonia recovery device of claim 1, wherein the electrolyte storage tank stores an anolyte comprising a sodium sulfate solution.
6. The ammonia recovery device according to claim 1, wherein the nitrate wastewater storage tank stores nitrate wastewater, and the concentration of nitrate in the nitrate wastewater is in the range of 500-50000mg N/L.
7. The ammonia recovery device according to claim 1, wherein an ammonia absorbing liquid is stored in the ammonia absorbing liquid storage tank, and the ammonia absorbing liquid includes one of a sulfuric acid solution, a hydrochloric acid solution, and a carbonic acid solution.
8. The ammonia recovery device according to claim 1, wherein the liquid inlet and the liquid outlet of the anode chamber are arranged oppositely, and the liquid inlet of the anode chamber is lower than the liquid outlet;
the liquid inlet and the liquid outlet of the cathode chamber are arranged oppositely, and the liquid inlet of the cathode chamber is lower than the liquid outlet;
the liquid inlet and the liquid outlet of the ammonia recovery chamber are arranged oppositely, and the liquid inlet of the ammonia recovery chamber is lower than the liquid outlet.
9. A method for recovering ammonia, characterized in that ammonia is recovered from nitrate containing wastewater by using the ammonia recovery apparatus according to any one of claims 1 to 8.
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