CN114950088B - Device for recycling treatment of nitrogen oxide waste gas by electrochemical reduction technology coupled with gas-liquid separation membrane technology, use method and application - Google Patents
Device for recycling treatment of nitrogen oxide waste gas by electrochemical reduction technology coupled with gas-liquid separation membrane technology, use method and application Download PDFInfo
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- CN114950088B CN114950088B CN202210505060.3A CN202210505060A CN114950088B CN 114950088 B CN114950088 B CN 114950088B CN 202210505060 A CN202210505060 A CN 202210505060A CN 114950088 B CN114950088 B CN 114950088B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
- B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/402—Dinitrogen oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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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
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- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention relates to a waste gas treatment device, in particular to a device for recycling treatment of nitrogen oxide waste gas by an electrochemical reduction technology coupled with a gas-liquid separation membrane technology, a use method and application thereof, comprising an electrochemical reactor formed by sequentially attaching a cathode air chamber, a gas diffusion cathode, a catholyte chamber, an anion exchange membrane, a gas diffusion anode and an anolyte chamber, and an ammonia recovery device communicated with the catholyte chamber through a conveying pipeline; the gas inlet system is communicated with the cathode gas chamber, the electrolyte liquid inlet system is communicated with the anolyte chamber, and the power supply is connected with the gas diffusion cathode and the gas diffusion anode; the ammonia recovery device is internally provided with a hollow fiber membrane, one side of the hollow fiber membrane is provided with electrolyte which is input by a catholyte chamber, and the other side of the hollow fiber membrane is provided with absorption liquid. Compared with the prior art, the method has the advantages of low energy consumption for treating the nitrogen oxide waste gas, high electrode activity, selectivity and recycling treatment efficiency, no secondary pollution and suitability for industrialized popularization.
Description
Technical Field
The invention relates to an exhaust gas treatment device, in particular to a device for recycling treatment of nitrogen oxide exhaust gas by using an electrochemical reduction technology coupled with a gas-liquid separation membrane technology, a use method and application thereof.
Background
In China, nitrogen oxide pollutants are mainly derived from flue gas emission in nonferrous smelting and thermal power industries, are one of important precursors causing environmental problems such as photochemical smog, acid rain, greenhouse effect and the like, and a large amount of emissions are seriously threatening the natural nitrogen circulation and human life safety. At present, the traditional selective catalytic reduction technology can realize harmless treatment from nitrogen oxides to nitrogen, but has the problems of huge energy consumption, secondary pollution and the like, and the application range is limited. More importantly, from the natural nitrogen circulation point of view, nitrogen oxides in the flue gas are also a nitrogen resource. Compared with the strategy of converting nitrogen oxides into nitrogen, the strategy of selectively converting nitrogen oxides into high-added-value ammonia and recycling ammonia is more in line with the national 'waste recycling' strategic requirements, and has important significance in practical application.
Compared with the traditional method, the electrochemical reduction technology has the advantages of simple operation, strong controllability, economy, applicability, mild reaction conditions and the like, and is expected to realize the selective conversion of nitrogen oxides to ammonia. Electrochemical reduction techniques, however, present challenges of low electrode activity and selectivity, and have a temporary limited range of applications. In addition, ammonia enrichment and recovery of nitrogen oxide conversion is an important link in nitrogen oxide recycling. In the actual electrochemical reduction of nitrogen oxides, the co-existence of anions/cations (chloride, sulfate and sodium) in the solution can interfere with the selective recovery of ammonia. The existing industrial ammonia distillation-stripping method has the problems of high energy consumption, incomplete release of ammonia in solution, low ammonia recovery rate (< 60%), and the like.
Disclosure of Invention
The invention aims to solve at least one of the problems, and provides a device for recycling the waste gas of nitrogen oxides by using an electrochemical reduction technology coupled with a gas-liquid separation membrane technology, a use method and application thereof, which realize the effective treatment of nitrogen oxide pollutants and the recycling of nitrogen oxides.
The aim of the invention is achieved by the following technical scheme:
the invention discloses a device for recycling nitrogen oxide waste gas by coupling an electrochemical reduction technology with a gas-liquid separation membrane technology, which comprises an electrochemical reactor and an ammonia recovery device, wherein the electrochemical reactor is formed by sequentially attaching a cathode air chamber, a gas diffusion cathode, a catholyte chamber, an anion exchange membrane, a gas diffusion anode and an anolyte chamber, and the ammonia recovery device is communicated with the catholyte chamber through a conveying pipeline;
the electrochemical reactor also comprises an air inlet system communicated with the cathode air chamber, an electrolyte inlet system communicated with the anolyte chamber and a power supply respectively connected with the gas diffusion cathode and the gas diffusion anode;
a hollow fiber membrane is arranged in the ammonia recovery device, one side of the hollow fiber membrane passes through electrolyte input from a catholyte chamber, and the other side of the hollow fiber membrane passes through absorption liquid;
the electrochemical reactor converts nitrogen oxides in the flue gas into ammonia, the ammonia is input into the ammonia recovery device along with electrolyte of the catholyte chamber through a conveying pipeline, and enters the absorption liquid through the hollow fiber membrane and then leaves the ammonia recovery device along with the absorption liquid, and the rest electrolyte is input back into the catholyte chamber.
Preferably, the gas diffusion cathode takes titanium foam as a substrate, and the surface of the gas diffusion cathode is loaded with transition metal monoatomic or nanocluster active substances; the aperture of the gas diffusion cathode is 50-100 mu m.
Preferably, the transition metal monoatomic or nanocluster active material comprises one or more of manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum and gold, and the mass loading is 0.01-20%.
Preferably, the electrolyte is one or more of sodium hydroxide, potassium hydroxide, sodium sulfate and potassium sulfate, and the concentration is 0.1-5mol/L; the absorption liquid is one or more of sulfuric acid, nitric acid and hydrochloric acid, and the concentration is 0.1-5mol/L.
Preferably, the gas diffusion anode is a ruthenium iridium coated titanium electrode, and the coating thickness is 8-15 mu m.
Preferably, the hollow fiber membrane is a hydrophobic porous membrane, the inner diameter of a membrane tube is 100 mu m-1mm, and the thickness of the membrane tube is 100 mu m-1mm.
Preferably, the hollow fiber membrane comprises a polypropylene fiber membrane, a polytetrafluoroethylene fiber membrane or a polyvinyl chloride hollow fiber membrane.
Preferably, the electrochemical reactor and the ammonia recovery device are in series connection to realize selective electrochemical conversion of nitrogen oxides into ammonia and synchronous recovery of the ammonia; the anolyte chamber and the catholyte chamber are both made of insulating materials, are tightly attached to the electrode and the anion exchange membrane, and ensure that the sealing effect of the device is free from leakage; the automatic electrolyte liquid inlet system and the air inlet system are composed of a pressurizing controller and a flow controller, and the flow rates of the waste gas and the electrolyte entering and discharging are controlled stably.
The second aspect of the invention discloses a method for using the device for recycling the waste gas of nitrogen oxides by coupling the electrochemical reduction technology with the gas-liquid separation membrane technology, wherein voltages are applied to a gas diffusion cathode and a gas diffusion Yang Jijian of an electrochemical reactor, the flue gas entering from an air inlet system is subjected to electrochemical reduction to form ammonia, the ammonia flows into a hollow fiber membrane of an ammonia recovery device along with electrolyte in a catholyte chamber, flows out of the ammonia recovery device along with absorption liquid through the hollow fiber membrane, and the rest of the electrolyte flows back into the catholyte chamber.
Preferably, the voltage is a direct current voltage of 0.5-36V; the flow rate of the flue gas is 0.001-10m/s; the flow rate of the electrolyte is 1-500mL/min; the flow rate of the absorption liquid is 1-500mL/min.
The third aspect of the invention discloses an application of the device for recycling treatment of nitrogen oxide waste gas by using the electrochemical reduction technology coupled with the gas-liquid separation membrane technology in treatment of nitrogen oxide waste gas.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the technical scheme, as the cathode adopts the porous gas diffusion electrode loaded with metal monoatoms or nanoclusters, nitrogen oxides can be selectively reduced into ammonia at a gas-liquid-solid three-phase interface, the ammonia enters the hollow fiber membrane component in the ammonia recovery device along with the catholyte, then the high-efficiency separation of ammonia in the electrolyte is realized by utilizing the ammonia evaporation pressure difference at two sides of the hollow fiber membrane, and finally the ammonia is absorbed by acid liquor in the ammonia recovery device. Therefore, the device for recycling the nitrogen oxide waste gas by coupling the electrochemical reduction technology with the gas-liquid separation membrane technology can realize the selective conversion of nitrogen oxide to ammonia and the synchronous recovery of ammonia, and is beneficial to realizing the control and recycling of nitrogen oxide pollutants. And the foam titanium-based metal monoatomic or nanocluster electrode has higher activity and better stability, and is favorable for improving the selectivity of converting nitrogen oxide pollutants into ammonia. And the hydrophobic hollow fiber membrane has higher ammonia recovery selectivity, thereby being beneficial to the improvement of ammonia recovery rate.
2. The device provided by the invention can effectively reduce the energy consumption for treating the nitrogen oxides in the industrial flue gas, has high electrode performance, can efficiently and selectively convert the nitrogen oxides into ammonia and efficiently recover the ammonia obtained by selectively converting the nitrogen oxides, has great significance for current environmental protection and waste gas resource utilization, and has great market application prospect.
3. The invention utilizes electrochemical reduction technology to selectively convert nitrogen oxides into ammonia at the three-phase interface of the gas diffusion cathode, and then the ammonia is pumped into an ammonia recovery device along with a catholyte pump and is recovered by absorption liquid through a hollow fiber membrane. The device for treating the waste gas containing the nitrogen oxides has the advantages of low energy consumption, high electrode activity and selectivity, high recycling efficiency of the nitrogen oxides, no secondary pollution and suitability for industrialized popularization.
Drawings
FIG. 1 is a schematic view of the structure of the device of the present invention;
FIG. 2 is a diagram of a titanium foam gas diffusion electrode carrying copper monoatoms;
FIG. 3 is an AC-TEM image of a copper monoatomic supported titanium foam gas diffusion electrode;
FIG. 4 is a graph of ammonia selectivity and ammonia production rate for a copper monoatomic supported titanium foam gas diffusion electrode to treat a simulated flue gas containing nitrogen oxides;
FIG. 5 is a diagram of recovered ammonia selectivity and efficiency for the apparatus of the present invention;
FIG. 6 is a graph of ammonia selectivity and ammonia production rate for a plant of the present invention treating simulated flue gas containing different concentrations of nitrogen oxides;
FIG. 7 is a graph of ammonia selectivity and ammonia production rate for a simulated flue gas containing 5% sulfur dioxide and 20% nitrogen oxides treated by the apparatus of the present invention;
FIG. 8 is a graph of ammonia recovery selectivity and efficiency for a simulated flue gas containing 5% sulfur dioxide and 20% nitrogen oxides treated by the apparatus of the present invention;
in the figure: 1-cathode gas cell; 2-a gas diffusion cathode; 3-catholyte compartment; 4-anion exchange membrane; 5-a gas diffusion anode; 6-an anolyte compartment; 7-ammonia recovery device; 8-conveying equipment.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those 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 not within the scope of protection claimed in the present invention.
The invention provides a device for recycling and treating nitrogen oxide waste gas by coupling an electrochemical reduction technology with a gas-liquid separation membrane technology, which is used for selectively converting nitrogen oxide pollutants into ammonia and synchronously recycling the ammonia, so as to realize recycling and utilization of the nitrogen oxide pollutants.
Referring to fig. 1, in an example of an apparatus for recycling waste gas containing nitrogen oxides by coupling an electrochemical reduction technology with a gas-liquid separation membrane technology according to the present invention, a serial apparatus for selectively converting nitrogen oxide pollutants into ammonia and synchronously recovering ammonia includes an electrochemical reactor and an ammonia recovery device 7, wherein the electrochemical reactor includes a power source, a cathode gas chamber 1, a gas diffusion cathode 2, a catholyte chamber 3, an anion exchange membrane 4, a gas diffusion anode 5 and an anolyte chamber 6, the gas diffusion cathode 2 is a porous foam titanium electrode loaded with an active material, the anion exchange membrane 4 is disposed between the catholyte chamber 3 and the gas diffusion anode 5, the gas diffusion anode 5 is a ruthenium iridium coated titanium electrode, and the ammonia recovery device 7 is a hollow fiber membrane module.
The power supply adopts a direct current power supply, a foam titanium gas diffusion electrode loaded with metal monoatoms or nanoclusters is used as a gas diffusion cathode 2, a ruthenium iridium coating electrode is used as a gas diffusion anode 5, an anion exchange membrane 4 is arranged between a catholyte chamber 3 and the gas diffusion anode 5, a cathode gas chamber 1, the gas diffusion cathode 2, the catholyte chamber 3, the anion exchange membrane 4, the gas diffusion anode 5 and an anolyte chamber 6 are clamped by multiple layers of materials, an airflow channel is arranged between the cathode gas chamber 1 and the gas diffusion cathode 2, an electrolyte channel is arranged between the gas diffusion anode 5 and the anolyte chamber 6, and meanwhile, the gas diffusion cathode 2 and the gas diffusion anode 5 are respectively connected with a negative electrode and a positive electrode of the direct current power supply through wires. The hollow fiber membrane module is used as an ammonia recovery device 7, and the catholyte chamber 3 and the ammonia recovery device 7 are connected in series through a pipeline. The gas diffusion cathode 2 adopts a porous gas diffusion electrode loaded with metal monoatoms or nanoclusters, and can selectively reduce nitrogen oxides to ammonia at a gas-liquid-solid three-phase interface. The ammonia recovery device 7 adopts a hollow fiber hydrophobic membrane and selects acid liquor as absorption liquid, and can efficiently separate and recover ammonia entering the hollow fiber membrane component along with catholyte.
Therefore, it can be understood that in the technical scheme of the invention, as the gas diffusion cathode 2 adopts the porous gas diffusion electrode loaded with metal monoatoms or nanoclusters, nitrogen oxides can be selectively reduced into ammonia at the gas-liquid-solid three-phase interface, the ammonia enters the hollow fiber membrane component in the ammonia recovery device 7 along with the catholyte, then the high-efficiency separation of ammonia in the electrolyte is realized by utilizing the ammonia evaporation pressure difference at two sides of the hollow fiber membrane, and finally the ammonia is absorbed by the acid liquor in the ammonia recovery device 7. Therefore, the device for selectively reducing the nitrogen oxides to ammonia and recycling ammonia can realize the selective conversion from the nitrogen oxides to the ammonia and the synchronous recycling of the ammonia, and is beneficial to realizing the control and the recycling of the nitrogen oxide pollutants. And the foam titanium-based metal monoatomic or nanocluster electrode has higher activity and better stability, and is favorable for improving the selectivity of converting nitrogen oxide pollutants into ammonia. And the hydrophobic hollow fiber membrane has higher ammonia recovery selectivity, thereby being beneficial to the improvement of ammonia recovery rate.
The device for recycling the nitrogen oxide waste gas by the electrochemical reduction technology coupled with the gas-liquid separation membrane technology further comprises a conveying device 8 and conveying pipelines (comprising a conveying pipeline for conveying flue gas, a conveying pipeline for conveying electrolyte, a conveying pipeline for conveying absorption liquid and a conveying pipeline for communicating the ammonia recovery device 7 and the catholyte chamber 3), wherein the conveying pipeline is communicated with the catholyte chamber 1 (an air inlet system), the conveying pipeline is communicated with the anolyte chamber 6 (an electrolyte liquid inlet system), the conveying pipelines are communicated with the catholyte chamber 3 and the ammonia recovery device 7, the conveying pipelines are respectively provided with the conveying device 8, and the conveying device 8 can be a fan, an air pump or a water pump according to passing fluid.
Optionally, the active component of the gas diffusion cathode 2 for achieving selective reduction of nitrogen oxides to ammonia is at least one of manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold monoatoms, nanoclusters. Manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold monoatoms and nanoclusters can be used as the active components of the gas diffusion cathode 2 for realizing the selective reduction of nitrogen oxides into ammonia, and one or more of the active components can be selected during use.
Alternatively, the hollow fiber membrane of the ammonia recovery device 7 is one of a polypropylene fiber membrane, a polytetrafluoroethylene fiber membrane, a polyvinyl chloride hollow fiber membrane, and other hydrophobic porous membranes. In assembling the ammonia recovery device 7, the hydrophobic porous membrane may be one of these substances.
Alternatively, the loading of the active material of the gas diffusion cathode 2 ranges from 0.01% to 20%. Such as an active loading of 0.01%, 0.1%, 1%, 5%, 10% or 20%. Preferably, the loading is 0.1% -1%, such as 0.1%, 0.2%, 0.4%, 0.8% or 1%.
In another aspect, the invention provides an application of the device in treating industrial flue gas containing nitrogen oxides.
The device provided by the invention can effectively reduce the energy consumption for treating the nitrogen oxides in the industrial flue gas, has high electrode performance, can efficiently and selectively convert the nitrogen oxides into ammonia and efficiently recover the ammonia obtained by selectively converting the nitrogen oxides, has great significance for current environmental protection and waste gas resource utilization, and has great market application prospect.
The invention also provides a using method of the electrochemical reduction technology coupled gas-liquid separation membrane technology for recycling the nitrogen oxide waste gas, which is applied to the device for recycling the nitrogen oxide waste gas by the electrochemical reduction technology coupled gas-liquid separation membrane technology, and comprises the following steps:
the flue gas containing the nitrogen oxide pollutants is introduced into the cathode air chamber 1, the electrolyte is introduced into the catholyte chamber 3 and the anolyte chamber 6, the absorption liquid is introduced into the ammonia recovery device 7, and a direct current voltage of 0.5V-36V is applied between the gas diffusion anode 5 and the gas diffusion cathode 2. The flow rate of the flue gas is controlled to be 0.001m/s-10m/s, and the flow rates of the electrolyte and the absorption liquid are controlled to be 1mL/min-500mL/min.
The DC voltage is preferably in the range of 2V to 5V, such as 2V, 3V, 4V or 5V. The nitrogen oxide pollutants are reduced to ammonia with high selectivity by adjusting the direct current voltage and the gas flow.
Here, the flow rates of the catholyte and the absorption liquid are preferably in the range of 50 to 250mL/min, for example, 50mL/min, 100mL/min, 150mL/min, 200mL/min or 250mL/min are used. The flow rates of the catholyte and the absorption liquid are adjusted so that the ammonia converted by the gas diffusion cathode 2 of the electrochemical reactor can be efficiently recovered in the ammonia recovery device 7.
The method for recycling the nitrogen oxide waste gas and the device thereof according to the present invention are described in detail below by means of specific examples.
Example 1
(1) Preparation of gas diffusion cathode 2: 20mg of copper chloride is dissolved in 5mL of ethanol, then the copper chloride ethanol solution is sprayed on the surface of porous foam titanium with the length of 2cm, the width of 2cm and the thickness of 0.68cm, and finally the solution is sprayed on the surface of porous foam titanium with the thickness of H 2 Calcining at 400 ℃ in Ar atmosphere to obtain the copper monoatomic foam titanium gas diffusion cathode 2. See fig. 2 and 3 for a physical view and an AC-TEM image of a copper monoatomic gas diffusion cathode 2.
(2) Assembly of electrochemical reactor and recovered ammonia tandem device: and (3) taking the electrode prepared in the step (1) as a gas diffusion cathode 2, taking an iridium ruthenium coating electrode as a gas diffusion anode 5, then clamping a cathode gas chamber 1, the gas diffusion cathode 2, a catholyte chamber 3, an anion exchange membrane 4, the gas diffusion anode 5 and an anolyte chamber 6, arranging a gas flow channel between the cathode gas chamber 1 and the gas diffusion cathode 2, arranging an electrolyte channel between the anolyte chamber 6 and the gas diffusion anode 5, and simultaneously respectively connecting the gas diffusion cathode 2 and the gas diffusion anode 5 with a cathode and an anode of a direct current power supply through wires to obtain the electrochemical reactor. The electrochemical reactor and the ammonia recovery series device can be obtained by connecting the ammonia recovery device 7 based on the hollow fiber membrane component with the catholyte chamber 3 of the electrochemical reactor through a conveying pipeline.
(3) A method for treating nitrogen oxide contaminants using a step (2) electrochemical reactor and a recovered ammonia serial device, comprising the steps of: and introducing gas containing nitrogen oxides into the cathode gas chamber 1, wherein the concentration of the nitrogen oxides is 20%, ar gas is used as balance gas, and the total flow is controlled at 100mL/min. The potassium sulfate electrolyte of 0.5mol/L was continuously fed into the catholyte chamber 3 and the anolyte chamber 6 by a conveying device 8 (water pump), at a flow rate of 100mL/min. Then, a direct current voltage is applied between the gas diffusion cathode 2 and the gas diffusion anode 5, and the concentration of ammonia in the electrolyte in the catholyte compartment 3 and the absorption liquid in the ammonia recovery device 7 is detected, the catalytic performance is shown in fig. 4, and the recovery efficiency and selectivity are shown in fig. 5.
As can be seen from FIG. 4, in the voltage range of 2-3V, the Faraday efficiency of selective reduction of nitrogen oxides to ammonia is over 90%, the ammonia production rate is gradually increased with the increase of the voltage, and the highest ammonia production rate can reach 1200mmol/h/cm, so that the catalytic efficiency of conversion of nitrogen oxides to ammonia is higher. As can be seen from fig. 5, the ammonia recovery efficiency of the series device was 90% or more and the selectivity was close to 100% in the continuous operation for 50 hours. The efficiency and selectivity of ammonia recovery of the series device are high.
Example 2
Ability of the device to handle simulated flue gas containing different nitrogen oxide concentrations: by using the tandem device assembled in example 1, nitrogen oxides containing 0%, 1%, 5%, 10% and 20% were introduced into the cathode gas chamber, ar gas was used as a balance gas, and the total flow rate was controlled at 100mL/min. Continuously introducing 0.5mol/L potassium sulfate electrolyte into the catholyte chamber and the anolyte chamber through a water pump, wherein the flow is 100mL/min. Then a direct voltage of 3V was applied between the cathode and the anode, and the ammonia concentration in the catholyte compartment electrolyte and the ammonia recovery unit absorption liquid was detected, the catalytic performance being seen in fig. 6.
As can be seen from FIG. 6, with the increase of the nitrogen oxide concentration in the simulated flue gas, the Faraday efficiency of the selective reduction of the electrode nitrogen oxide into ammonia is over 90%, the ammonia production rate is gradually increased, and the treatment capacity of the device for nitrogen oxides with different concentrations is higher.
Example 3
Testing the anti-jamming capability of the device: by using the series device assembled in example 1, 5% sulfur dioxide and 20% nitrogen oxide were introduced into the cathode gas chamber, ar gas was used as balance gas, and the total flow was controlled at 100mL/min. Continuously introducing 0.5mol/L potassium sulfate electrolyte into the catholyte chamber and the anolyte chamber through a water pump, wherein the flow is 100mL/min. Then a direct voltage is applied between the cathode and the anode, and the ammonia concentration in the catholyte compartment electrolyte and the ammonia recovery unit absorption liquid is detected, the catalytic performance is shown in fig. 7, and the recovery efficiency and selectivity are shown in fig. 8.
From fig. 7 and fig. 8, it can be seen that in the voltage range of 2-3V, the faraday efficiency and the ammonia production rate of the device for selectively converting nitrogen oxides into ammonia and the ammonia recovery efficiency and selectivity of the device are not greatly affected by the existence of sulfur dioxide in the simulated flue gas, and the anti-interference capability of the device is good.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The device for recycling the nitrogen oxide waste gas by using the electrochemical reduction technology coupled with the gas-liquid separation membrane technology is characterized by comprising an electrochemical reactor formed by sequentially attaching a cathode air chamber (1), a gas diffusion cathode (2), a catholyte chamber (3), an anion exchange membrane (4), a gas diffusion anode (5) and an anolyte chamber (6) and an ammonia recovery device (7) communicated with the catholyte chamber (3) through a conveying pipeline;
the electrochemical reactor also comprises an air inlet system communicated with the cathode air chamber (1), an electrolyte inlet system communicated with the anolyte chamber (6) and a power supply respectively connected with the gas diffusion cathode (2) and the gas diffusion anode (5); the gas diffusion cathode (2) takes foam titanium as a substrate, and the surface of the gas diffusion cathode is loaded with transition metal monoatomic or nanocluster active substances to enable nitric oxide to be selectively reduced into ammonia;
the electrochemical reactor and the ammonia recovery device (7) are mutually connected in series; a hollow fiber membrane is arranged in the ammonia recovery device (7), one side of the hollow fiber membrane passes through electrolyte input from the catholyte chamber (3), and the other side of the hollow fiber membrane passes through absorption liquid;
the electrochemical reactor converts nitrogen oxides in the flue gas into ammonia, the ammonia is input into the ammonia recovery device (7) along with electrolyte of the catholyte chamber (3) through a conveying pipeline, and enters absorption liquid through the hollow fiber membrane and then leaves the ammonia recovery device (7) along with the absorption liquid, and the rest electrolyte is input back into the catholyte chamber (3).
2. The device for recycling treatment of nitrogen oxide waste gas by coupling electrochemical reduction technology with gas-liquid separation membrane technology according to claim 1, wherein the pore diameter of the gas diffusion cathode (2) is 50-100 μm.
3. The device for recycling treatment of nitrogen oxide waste gas by coupling electrochemical reduction technology with gas-liquid separation membrane technology according to claim 2, wherein the transition metal single-atom or nanocluster active material comprises one or more of manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum and gold, and the mass loading is 0.01-20%.
4. The device for recycling treatment of nitrogen oxide waste gas by using an electrochemical reduction technology coupled with a gas-liquid separation membrane technology according to claim 1, wherein the electrolyte is one or more of sodium hydroxide, potassium hydroxide, sodium sulfate and potassium sulfate, and the concentration is 0.1-5mol/L; the absorption liquid is one or more of sulfuric acid, nitric acid and hydrochloric acid, and the concentration is 0.1-5mol/L.
5. The device for recycling treatment of nitrogen oxide waste gas by using the electrochemical reduction technology coupled with the gas-liquid separation membrane technology according to claim 1, wherein the gas diffusion anode (5) is a ruthenium iridium coating titanium electrode, and the coating thickness is 8-15 μm.
6. The device for recycling treatment of nitrogen oxide waste gas by coupling electrochemical reduction technology with gas-liquid separation membrane technology according to claim 1, wherein the hollow fiber membrane is a hydrophobic porous membrane, the inner diameter of the membrane tube is 100 μm-1mm, and the thickness of the membrane tube is 100 μm-1mm.
7. The device for recycling treatment of nitrogen oxide waste gas by coupling electrochemical reduction technology with gas-liquid separation membrane technology according to claim 6, wherein the hollow fiber membrane comprises a polypropylene fiber membrane, a polytetrafluoroethylene fiber membrane or a polyvinyl chloride hollow fiber membrane.
8. A method of using the device for the electrochemical reduction technology coupled with the gas-liquid separation membrane technology for recycling treatment of nitrogen oxide waste gas as claimed in any one of claims 1 to 7, characterized in that a voltage is applied between a gas diffusion cathode (2) and a gas diffusion anode (5) of an electrochemical reactor, the flue gas entering from an air inlet system is electrochemically reduced to form ammonia, the ammonia flows into a hollow fiber membrane of an ammonia recovery device (7) along with electrolyte in a catholyte chamber (3), and flows out of the ammonia recovery device (7) along with absorption liquid through the hollow fiber membrane, and the rest of electrolyte flows back into the catholyte chamber (3).
9. The method for using the device for recycling the nitrogen oxide waste gas by using the electrochemical reduction technology coupled with the gas-liquid separation membrane technology according to claim 8, wherein the voltage is a direct-current voltage of 0.5-36V; the flow rate of the flue gas is 0.001-10m/s; the flow rate of the electrolyte is 1-500mL/min; the flow rate of the absorption liquid is 1-500mL/min.
10. Use of an apparatus for the treatment of nitrogen oxide exhaust gas according to any one of claims 1 to 7 by means of electrochemical reduction coupled with gas-liquid separation membrane technology.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5354436A (en) * | 1989-08-07 | 1994-10-11 | European Atomic Energy Community (Euratom) | Process for removing nitrogen compounds from a liquid |
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| CN101327393A (en) * | 2007-06-20 | 2008-12-24 | 天津工业大学 | Equipment and method for processing gas absorbed by film |
| JP2015213888A (en) * | 2014-05-13 | 2015-12-03 | 株式会社Ihi | Exhaust gas treatment method and exhaust gas treatment device |
| CN108114599A (en) * | 2017-12-25 | 2018-06-05 | 中国科学技术大学 | It is a kind of based on salt error the electrodialysis reversal of production soda acid to be driven to couple bipolar membranous system and its production method |
| CN112981438A (en) * | 2021-02-02 | 2021-06-18 | 碳能科技（北京）有限公司 | CO2System for producing synthesis gas by electrolysis |
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| JPH09276646A (en) * | 1996-04-10 | 1997-10-28 | Toshiba Corp | Reduction of nitrogen oxide |
| US5709789A (en) * | 1996-10-23 | 1998-01-20 | Sachem, Inc. | Electrochemical conversion of nitrogen containing gas to hydroxylamine and hydroxylammonium salts |
| KR102250321B1 (en) * | 2018-06-29 | 2021-05-10 | 한국화학연구원 | Electrochemical system for producing ammonia from nitrogen oxides and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5354436A (en) * | 1989-08-07 | 1994-10-11 | European Atomic Energy Community (Euratom) | Process for removing nitrogen compounds from a liquid |
| JPH09271781A (en) * | 1996-04-08 | 1997-10-21 | Toshiba Corp | Method of removing nitrogen from waste water |
| CN101327393A (en) * | 2007-06-20 | 2008-12-24 | 天津工业大学 | Equipment and method for processing gas absorbed by film |
| JP2015213888A (en) * | 2014-05-13 | 2015-12-03 | 株式会社Ihi | Exhaust gas treatment method and exhaust gas treatment device |
| CN108114599A (en) * | 2017-12-25 | 2018-06-05 | 中国科学技术大学 | It is a kind of based on salt error the electrodialysis reversal of production soda acid to be driven to couple bipolar membranous system and its production method |
| CN112981438A (en) * | 2021-02-02 | 2021-06-18 | 碳能科技（北京）有限公司 | CO2System for producing synthesis gas by electrolysis |
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