CN114950088A - Device for resourcefully treating nitrogen oxide waste gas by coupling electrochemical reduction technology with gas-liquid separation membrane technology, use method and application - Google Patents
Device for resourcefully treating nitrogen oxide waste gas by coupling electrochemical reduction technology with gas-liquid separation membrane technology, use method and application Download PDFInfo
- Publication number
- CN114950088A CN114950088A CN202210505060.3A CN202210505060A CN114950088A CN 114950088 A CN114950088 A CN 114950088A CN 202210505060 A CN202210505060 A CN 202210505060A CN 114950088 A CN114950088 A CN 114950088A
- Authority
- CN
- China
- Prior art keywords
- gas
- cathode
- ammonia
- nitrogen oxide
- chamber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- 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 resourcefully treating nitrogen oxide waste gas by coupling an electrochemical reduction technology with a gas-liquid separation membrane technology, a use method and application, and the device comprises an electrochemical reactor and an ammonia recovery device, wherein the electrochemical reactor is formed by sequentially attaching a cathode gas chamber, a gas diffusion cathode, a cathode liquid chamber, an anion exchange membrane, a gas diffusion anode and an anode liquid chamber, and the ammonia recovery device is communicated with the cathode liquid chamber through a conveying pipeline; the gas diffusion device also comprises a gas inlet system communicated with the cathode gas chamber, an electrolyte inlet system communicated with the anode liquid chamber and a power supply 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 the electrolyte input from the catholyte chamber, and the other side of the hollow fiber membrane passes through the 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 industrial popularization.
Description
Technical Field
The invention relates to a waste gas treatment device, in particular to a device for resourcefully treating nitrogen oxide waste gas by coupling an electrochemical reduction technology with a gas-liquid separation membrane technology, a use method and application.
Background
In China, nitrogen oxide pollutants mainly come from smoke emission of nonferrous smelting and thermal power industries, are one of important precursors causing photochemical smog, acid rain, greenhouse effect and other environmental problems, and the large amount of emission of the nitrogen oxide pollutants seriously threatens natural nitrogen circulation and human life safety. At present, the traditional selective catalytic reduction technology can realize the 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 viewpoint of natural nitrogen circulation, nitrogen oxides in the flue gas are also a nitrogen resource. Compared with the strategy of converting the nitrogen oxide into the nitrogen, the strategy of selectively converting the nitrogen oxide into the ammonia with high added value and recovering the ammonia better meets the strategic requirements of 'waste recycling' in China, 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 the nitrogen oxide to the ammonia. However, electrochemical reduction techniques face the problem of low electrode activity and selectivity, and the range of applications is temporarily limited. In addition, the enrichment and recovery of ammonia converted from nitrogen oxides are important links for recycling nitrogen oxides. In the actual electrochemical reduction of nitrogen oxides, the solution co-existence of anions/cations (chloride, sulfate and sodium) can interfere with the selective recovery of ammonia. The industrial ammonia distillation-stripping method at present has the problems of large 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, a using method and application for resourcefully treating nitrogen oxide waste gas by coupling an electrochemical reduction technology and a gas-liquid separation membrane technology, so that nitrogen oxide pollutants are effectively treated, and the resource utilization of nitrogen oxides is realized.
The purpose of the invention is realized by the following technical scheme:
the invention discloses a device for resourcefully treating 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 laminating a cathode gas chamber, a gas diffusion cathode, a cathode liquid chamber, an anion exchange membrane, a gas diffusion anode and an anode liquid chamber;
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 the electrolyte input from the catholyte chamber, and the other side of the hollow fiber membrane passes through the absorption liquid;
the electrochemical reactor converts nitrogen oxides in the flue gas into ammonia, the ammonia is conveyed into the ammonia recovery device along with electrolyte in the catholyte chamber through a conveying pipeline, enters the absorption liquid through the hollow fiber membrane and then leaves the ammonia recovery device along with the absorption liquid, and the residual electrolyte is conveyed back to the catholyte chamber.
Preferably, the gas diffusion cathode takes titanium foam as a substrate, and a transition metal monoatomic or nanocluster active substance is loaded on the surface of the gas diffusion cathode; the aperture of the gas diffusion cathode is 50-100 μm.
Preferably, the transition metal monoatomic or nanocluster active material includes one or more of manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold at a mass loading of 0.01-20%.
Preferably, the electrolyte is one or more of sodium hydroxide, potassium hydroxide, sodium sulfate and potassium sulfate, and the concentration is 0.1-5 mol/L; the absorption liquid is one or more of sulfuric acid, nitric acid and hydrochloric acid, and the concentration is 0.1-5 mol/L.
Preferably, the gas diffusion anode is a ruthenium iridium coated titanium electrode, and the thickness of the coating is 8-15 μm.
Preferably, 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-1 mm.
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 work in series to realize the selective electrochemical conversion of nitrogen oxides into ammonia and the synchronous recovery of ammonia; the anolyte chamber and the catholyte chamber are both made of insulating materials and are tightly attached to the electrodes and the anion exchange membrane, so that the sealing effect of the device is ensured to be leak-free; the automatic electrolyte inlet system and the air inlet system are composed of a pressurization controller and a flow controller, and the flow speed of waste gas and electrolyte entering and discharging is stably controlled.
The invention also discloses a method for using the device for resourcefully treating the nitrogen oxide waste gas by coupling the electrochemical reduction technology with the gas-liquid separation membrane technology, which is characterized in that voltage is applied between a gas diffusion cathode and a gas diffusion anode of an electrochemical reactor, flue gas entering from a gas inlet system is electrochemically reduced to form ammonia, the ammonia flows into a hollow fiber membrane of an ammonia recovery device along with electrolyte in a cathode liquid chamber and flows out of the ammonia recovery device along with absorption liquid through the hollow fiber membrane, and the residual electrolyte flows back to the cathode liquid chamber.
Preferably, the voltage is 0.5-36V DC voltage; the flow velocity of the flue gas is 0.001-10 m/s; the flow rate of the electrolyte is 1-500 mL/min; the flow rate of the absorption liquid is 1-500 mL/min.
The invention also discloses an application of the device for recycling nitrogen oxide waste gas by coupling the electrochemical reduction technology with the gas-liquid separation membrane technology in nitrogen oxide waste gas treatment.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the technical scheme, the cathode adopts the porous gas diffusion electrode loaded with metal monoatomic atoms 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 catholyte, then the high-efficiency separation of the 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 resourcefully treating the nitrogen oxide waste gas by coupling the electrochemical reduction technology with the gas-liquid separation membrane technology can realize the selective conversion from the nitrogen oxide to ammonia and the synchronous recovery of ammonia, and is favorable for realizing the control and resource utilization of nitrogen oxide pollutants. And the foamed titanium-based metal monoatomic or nanocluster electrode has high activity and good stability, and is beneficial to improving the selectivity of converting nitrogen oxide pollutants into ammonia. And the hydrophobic hollow fiber membrane has higher ammonia recovery selectivity, and is beneficial to improving the ammonia recovery rate.
2. The device provided by the invention can effectively reduce the energy consumption for treating the nitric oxide in the industrial flue gas, has high electrode performance, can efficiently and selectively convert the nitric oxide into ammonia and efficiently recover the ammonia obtained by selectively converting the nitric oxide, has important significance for current environmental protection and waste gas resource utilization, and also has great market application prospect.
3. The invention utilizes electrochemical reduction technology to selectively convert nitrogen oxides into ammonia at a three-phase interface of a gas diffusion cathode, and then the ammonia is pumped into an ammonia recovery device along with catholyte and is recovered by absorption liquid through a hollow fiber membrane. The device provided by the invention is used for treating the waste gas containing the nitrogen oxides, so that the energy consumption is low, the electrode activity and selectivity are high, the recycling treatment efficiency of the nitrogen oxides is high, no secondary pollution is caused, and the device is suitable for industrial popularization.
Drawings
FIG. 1 is a schematic diagram of the structure of the apparatus of the present invention;
FIG. 2 is a schematic diagram of a copper monoatomic supported titanium foam gas diffusion electrode;
FIG. 3 is an AC-TEM image of a titanium foam gas diffusion electrode loaded with copper monoatomic atoms;
FIG. 4 is a graph of ammonia selectivity and ammonia production rate for copper monatomic loaded titanium foam gas diffusion electrode treatment of nitrogen oxide-containing simulated flue gas;
FIG. 5 is a graph of recovered ammonia selectivity and efficiency for an apparatus of the present invention;
FIG. 6 is a graph of ammonia selectivity and ammonia production rate for simulated flue gas containing different concentrations of NOx treated by the apparatus of the present invention;
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 the recovery ammonia selectivity and efficiency of the apparatus of the present invention for treating a simulated flue gas containing 5% sulfur dioxide and 20% nitrogen oxides;
in the figure: 1-a cathode gas chamber; 2-a gas diffusion cathode; 3-a catholyte compartment; 4-an anion exchange membrane; 5-a gas diffusion anode; 6-anolyte compartment; 7-an ammonia recovery unit; 8-conveying equipment.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, technical solutions between the embodiments may be combined with each other, but must be based on the realization of the technical solutions by a person skilled in the art, and when the technical solutions are contradictory to each other or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The invention provides a device for recycling nitrogen oxide waste gas by coupling an electrochemical reduction technology with a gas-liquid separation membrane technology, which is used for selective conversion of nitrogen oxide pollutants into ammonia and synchronous recovery of ammonia, and realizes resource utilization of the nitrogen oxide pollutants.
Referring to fig. 1, in an embodiment of an apparatus for recycling nitrogen oxide waste gas 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 recycling ammonia includes an electrochemical reactor and an ammonia recycling apparatus 7, the electrochemical reactor includes a power supply, a cathode gas chamber 1, a gas diffusion cathode 2, a cathode liquid chamber 3, an anion exchange membrane 4, a gas diffusion anode 5, and an anode liquid chamber 6, the gas diffusion cathode 2 is a porous titanium foam electrode loaded with active materials, the anion exchange membrane 4 is disposed between the cathode liquid chamber 3 and the gas diffusion anode 5, the gas diffusion anode 5 is a ruthenium iridium coated titanium electrode, and the ammonia recycling apparatus 7 is a hollow fiber membrane module.
The power supply adopts a direct current power supply, a foamed titanium gas diffusion electrode loaded with metal single atoms 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 cathode liquid chamber 3 and the gas diffusion anode 5, a cathode gas chamber 1, the gas diffusion cathode 2, the cathode liquid chamber 3, the anion exchange membrane 4, the gas diffusion anode 5 and an anode liquid chamber 6 are clamped by multi-layer 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 anode liquid chamber 6, and 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 leads. A 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 monoatomic or nanoclusters, and can selectively reduce nitrogen oxides into 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 the catholyte.
Therefore, it can be understood that, in the technical solution of the present invention, since the gas diffusion cathode 2 employs the porous gas diffusion electrode loaded with metal monoatomic atoms or nanoclusters, nitrogen oxides can be selectively reduced to ammonia at the gas-liquid-solid three-phase interface, the ammonia enters the hollow fiber membrane module in the ammonia recovery device 7 along with the catholyte, then the ammonia is efficiently separated from the electrolyte by using the ammonia evaporation pressure difference at both sides of the hollow fiber membrane, and finally the ammonia is absorbed by the acid solution in the ammonia recovery device 7. Therefore, the device for coupling ammonia recovery by selectively reducing the nitrogen oxide into the ammonia can realize the selective conversion from the nitrogen oxide to the ammonia and the synchronous recovery of the ammonia, and is favorable for realizing the control and resource utilization of nitrogen oxide pollutants. And the foamed titanium-based metal monoatomic or nanocluster electrode has high activity and good stability, and is beneficial to improving the selectivity of converting nitrogen oxide pollutants into ammonia. And the hydrophobic hollow fiber membrane has higher ammonia recovery selectivity, and is beneficial to improving the ammonia recovery rate.
It should be noted that the device for resourcefully treating nitrogen oxide waste gas by coupling the electrochemical reduction technology with the gas-liquid separation membrane technology further comprises a conveying device 8 and a conveying pipeline (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 with 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 inlet system), the conveying pipeline is communicated with the catholyte chamber 3 and the ammonia recovery device 7, the conveying pipeline is provided with the conveying device 8, and the conveying device 8 can be selected as a fan, an air pump or a water pump according to a passing fluid.
Alternatively, the active ingredient of the gas diffusion cathode 2 that effects 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 monatomic, nanoclusters. Manganese, iron, cobalt, nickel, copper, molybdenum, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold monatomic, nanocluster can all be as gas diffusion cathode 2 realizes the selective reduction of nitrogen oxide to the active ingredient of ammonia, one or more of them can be selected when using.
Alternatively, the hollow fiber membrane of the ammonia recovery device 7 is one of hydrophobic porous membranes such as a polypropylene fiber membrane, a polytetrafluoroethylene fiber membrane, and a polyvinyl chloride hollow fiber membrane. In assembling the ammonia recovery device 7, one of these substances can be selected as the hydrophobic porous membrane.
Alternatively, the loading amount of the active material of the gas diffusion cathode 2 ranges from 0.01% to 20%. For example, the loading of active material is 0.01%, 0.1%, 1%, 5%, 10% or 20%. Preferably, the loading is 0.1% to 1%, such as 0.1%, 0.2%, 0.4%, 0.8% or 1%.
The invention also provides application of the device in treating the industrial flue gas containing the nitrogen oxides.
The device provided by the invention can effectively reduce the energy consumption for treating the nitric oxide in the industrial flue gas, has high electrode performance, can efficiently and highly selectively convert the nitric oxide into ammonia and efficiently recover ammonia obtained by selectively converting the nitric oxide, has important significance for current environmental protection and waste gas resource utilization, and also has great market application prospect.
The invention also provides a use method for resourcefully treating the nitrogen oxide waste gas by coupling the electrochemical reduction technology with the gas-liquid separation membrane technology, which is applied to the device for resourcefully treating the nitrogen oxide waste gas by coupling the electrochemical reduction technology with the gas-liquid separation membrane technology and comprises the following steps:
introducing flue gas containing nitrogen oxide pollutants into a cathode gas chamber 1, introducing electrolyte into a cathode liquid chamber 3 and an anode liquid chamber 6, introducing absorption liquid into an ammonia recovery device 7, and applying a direct current voltage of 0.5-36V between a gas diffusion anode 5 and a gas diffusion cathode 2. Controlling the flow rate range of the flue gas to be 0.001-10m/s, and controlling the flow rate range of the electrolyte and the absorption liquid to be 1-500 mL/min.
The DC voltage range is preferably 2V-5V, for example, 2V, 3V, 4V or 5V. The nitrogen oxide pollutants are reduced into ammonia with high selectivity by adjusting direct current voltage and gas flow.
Here, the flow rates of the catholyte and the absorption liquid are preferably in the range of 50-250mL/min, for example, flow rates of 50mL/min, 100mL/min, 150mL/min, 200mL/min or 250mL/min are used. The ammonia converted by the electrochemical reactor gas diffusion cathode 2 is efficiently recovered in the ammonia recovery unit 7 by adjusting the flow rates of the catholyte and the absorption liquid.
The method for recycling nitrogen oxide waste gas and the device thereof according to the present invention will be described in detail by the following embodiments.
Example 1
(1) Preparation of gas diffusion cathode 2: dissolving 20mg of copper chloride in 5mL of ethanol, spraying the ethanol solution of copper chloride on the surface of porous titanium foam with the thickness of 2cm (length) × 2cm (width) × 0.68cm (thickness), and spraying the solution on the surface of porous titanium foam with the thickness of H 2 Calcining at 400 ℃ in an Ar atmosphere to obtain the copper monatomic titanium foam gas diffusion cathode 2. Physical images and AC-TEM images of the gas diffusion cathode 2 with copper monoatomic ions are shown in fig. 2 and 3.
(2) Assembly of electrochemical reactor and ammonia recovery cascade: and (2) 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, clamping a cathode gas chamber 1, the gas diffusion cathode 2, a cathode liquid chamber 3, an anion exchange membrane 4, the gas diffusion anode 5 and an anode liquid 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 anode liquid 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 negative electrode and a positive electrode of a direct current power supply through leads to obtain the electrochemical reactor. The ammonia recovery device 7 based on the hollow fiber membrane module is connected with the catholyte chamber 3 of the electrochemical reactor by a conveying pipeline, so that the electrochemical reactor and the serial device for recovering ammonia can be obtained.
(3) The method for treating nitrogen oxide pollutants by using the electrochemical reactor and the ammonia recovery series device in the step (2) comprises the following steps of: and (3) introducing gas containing nitrogen oxide into the cathode gas chamber 1, wherein the concentration of the nitrogen oxide is 20%, Ar gas is used as balance gas, and the total flow is controlled at 100 mL/min. 0.5mol/L potassium sulfate electrolyte is continuously introduced into the catholyte chamber 3 and the anolyte chamber 6 through a conveying device 8 (a water pump), and the flow rate is 100 mL/min. Then, a direct current voltage is applied between the gas diffusion cathode 2 and the gas diffusion anode 5, and the ammonia concentration in the electrolyte in the catholyte chamber 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 efficiencies of selective reduction of nitrogen oxides to ammonia are all above 90%, the ammonia production rate gradually increases with the increase of voltage, the highest ammonia production rate can reach 1200mmol/h/cm, and the catalytic efficiency of conversion of nitrogen oxides to ammonia is high. As can be seen from fig. 5, the ammonia recovery efficiency of the series apparatus was 90% or more and the selectivity was close to 100% within 50 hours of continuous operation. The efficiency and the selectivity of the serial device for recovering ammonia are higher.
Example 2
Capacity of the device to treat simulated flue gas containing different nitrogen oxide concentrations: using the tandem device assembled in example 1, nitrogen oxides containing 0%, 1%, 5%, 10%, and 20% were introduced into a cathode gas chamber, and Ar gas was used as an equilibrium gas, and the total flow rate was controlled to 100 mL/min. 0.5mol/L potassium sulfate electrolyte is continuously introduced into a catholyte chamber and an anolyte chamber through a water pump, and the flow rate is 100 mL/min. Then, a direct current voltage of 3V was applied between the cathode and the anode, and the ammonia concentration in the catholyte chamber electrolyte and the ammonia recovery device absorbent was detected, and the catalytic performance is shown in fig. 6.
As can be seen from FIG. 6, with the increase of the concentration of the nitrogen oxides in the simulated flue gas, the Faraday efficiencies of the selective reduction of the nitrogen oxides of the electrodes to ammonia are all above 90%, the ammonia production rate is gradually increased, and the treatment capacities of the device to the nitrogen oxides with different concentrations are high.
Example 3
And (3) testing the anti-interference capability of the device: the series apparatus assembled in example 1 was used to introduce 5% sulfur dioxide and 20% nitrogen oxide into the cathode gas chamber, with Ar gas as the balance gas, and the total flow rate was controlled at 100 mL/min. 0.5mol/L potassium sulfate electrolyte is continuously introduced into a catholyte chamber and an anolyte chamber through a water pump, and the flow rate is 100 mL/min. Then, a direct current voltage was applied between the cathode and the anode, and the ammonia concentration in the catholyte chamber electrolyte and the ammonia recovery device absorbent was detected, and the catalytic performance was shown in fig. 7, and the recovery efficiency and selectivity were shown in fig. 8.
As can be seen from FIGS. 7 and 8, in the voltage range of 2-3V, the influence of the existence of sulfur dioxide in the simulated flue gas on the Faraday efficiency and the ammonia production rate of the device for selectively converting nitrogen oxide into ammonia and the ammonia recovery efficiency and selectivity of the device is small, and the anti-interference capability of the device is good.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, 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 embodiments, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.
Claims (10)
1. A device for resourcefully treating nitrogen oxide waste gas by coupling an electrochemical reduction technology with a gas-liquid separation membrane technology is characterized by comprising an electrochemical reactor and an ammonia recovery device (7), wherein the electrochemical reactor is formed by sequentially attaching a cathode gas chamber (1), a gas diffusion cathode (2), a cathode liquid chamber (3), an anion exchange membrane (4), a gas diffusion anode (5) and an anode liquid chamber (6), and the ammonia recovery device is communicated with the cathode liquid 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 anode liquid chamber (6) and a power supply respectively connected with the gas diffusion cathode (2) and the gas diffusion anode (5);
a hollow fiber membrane is arranged in the ammonia recovery device (7), one side of the hollow fiber membrane passes through the electrolyte input from the catholyte chamber (3), and the other side of the hollow fiber membrane passes through the absorption liquid;
the electrochemical reactor converts nitrogen oxides in the flue gas into ammonia, the ammonia is conveyed into the ammonia recovery device (7) along with electrolyte in the catholyte chamber (3) through a conveying pipeline, enters the 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 conveyed back to the catholyte chamber (3).
2. The device for resource treatment of nitrogen oxide waste gas by coupling electrochemical reduction technology with gas-liquid separation membrane technology according to claim 1, wherein the gas diffusion cathode (2) takes titanium foam as a substrate, and a transition metal monoatomic or nanocluster active substance is loaded on the surface of the gas diffusion cathode; the aperture of the gas diffusion cathode (2) is 50-100 μm.
3. The device for resource 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 monoatomic or nanocluster active substance 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 resource treatment of nitrogen oxide waste gas by coupling electrochemical reduction technology with 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 0.1-5 mol/L; the absorption liquid is one or more of sulfuric acid, nitric acid and hydrochloric acid, and the concentration is 0.1-5 mol/L.
5. The device for resource treatment of nitrogen oxide waste gas by coupling electrochemical reduction technology with gas-liquid separation membrane technology according to claim 1, characterized in that the gas diffusion anode (5) is a ruthenium iridium coated titanium electrode, and the coating thickness is 8-15 μm.
6. The device for resource 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-1 mm.
7. The device for resource 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 polypropylene fiber membrane, polytetrafluoroethylene fiber membrane or polyvinyl chloride hollow fiber membrane.
8. A method for using the device for resource treatment of nitrogen oxide waste gas by coupling the electrochemical reduction technology with the gas-liquid separation membrane technology according to any one of claims 1 to 7, wherein a voltage is applied between the gas diffusion cathode (2) and the gas diffusion anode (5) of the electrochemical reactor, flue gas entering from the gas inlet system is electrochemically reduced to form ammonia, the ammonia flows into the hollow fiber membrane of the ammonia recovery device (7) along with the electrolyte in the catholyte chamber (3) and flows out of the ammonia recovery device (7) along with the absorption liquid through the hollow fiber membrane, and the residual electrolyte flows back to the catholyte chamber (3).
9. The use method of the device for resource treatment of nitrogen oxide waste gas by coupling the electrochemical reduction technology with the gas-liquid separation membrane technology according to claim 8, wherein the voltage is 0.5-36V DC voltage; the flow velocity of the flue gas is 0.001-10 m/s; the flow rate of the electrolyte is 1-500 mL/min; the flow rate of the absorption liquid is 1-500 mL/min.
10. The application of the device for resource treatment of nitrogen oxide waste gas by coupling the electrochemical reduction technology and the gas-liquid separation membrane technology according to any one of claims 1 to 7 in nitrogen oxide waste gas treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210505060.3A CN114950088B (en) | 2022-05-10 | 2022-05-10 | Device for recycling treatment of nitrogen oxide waste gas by electrochemical reduction technology coupled with gas-liquid separation membrane technology, use method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210505060.3A CN114950088B (en) | 2022-05-10 | 2022-05-10 | Device for recycling treatment of nitrogen oxide waste gas by electrochemical reduction technology coupled with gas-liquid separation membrane technology, use method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114950088A true CN114950088A (en) | 2022-08-30 |
| CN114950088B CN114950088B (en) | 2023-09-29 |
Family
ID=82980682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210505060.3A Active CN114950088B (en) | 2022-05-10 | 2022-05-10 | Device for recycling treatment of nitrogen oxide waste gas by electrochemical reduction technology coupled with gas-liquid separation membrane technology, use method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114950088B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116514234A (en) * | 2023-06-28 | 2023-08-01 | 广东工业大学 | Stack type electrochemical ammonia recovery device and method loaded with pulsed electric field |
Citations (9)
| 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 |
| 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 |
| 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 |
| US20200002180A1 (en) * | 2018-06-29 | 2020-01-02 | Korea Research Institute Of Chemical Technology | Electrochemical system for producing ammonia from nitrogen oxides and preparation method thereof |
| 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 |
-
2022
- 2022-05-10 CN CN202210505060.3A patent/CN114950088B/en active Active
Patent Citations (9)
| 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 |
| 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 |
| 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 |
| US20200002180A1 (en) * | 2018-06-29 | 2020-01-02 | Korea Research Institute Of Chemical Technology | Electrochemical system for producing ammonia from nitrogen oxides and preparation method thereof |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116514234A (en) * | 2023-06-28 | 2023-08-01 | 广东工业大学 | Stack type electrochemical ammonia recovery device and method loaded with pulsed electric field |
| CN116514234B (en) * | 2023-06-28 | 2023-09-01 | 广东工业大学 | Stack type electrochemical ammonia recovery device and method loaded with pulsed electric field |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114950088B (en) | 2023-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113774416B (en) | Gas diffusion cathode and electrochemical reactor for in-situ production of hydrogen peroxide | |
| KR102250321B1 (en) | Electrochemical system for producing ammonia from nitrogen oxides and preparation method thereof | |
| CN109487081B (en) | Lithium extraction unit using flow electrode, extension device and continuous operation method | |
| MX2012011482A (en) | Selective catalytic reduction via electrolysis of urea. | |
| JP2013541662A (en) | Selective catalytic reduction by electrolysis of urea. | |
| CN114950088B (en) | Device for recycling treatment of nitrogen oxide waste gas by electrochemical reduction technology coupled with gas-liquid separation membrane technology, use method and application | |
| KR101366183B1 (en) | Redox fuel cell using by ferric-edta(ehylenediaminetetraacetic acid) and nitrogen oxide(no) separation using the same | |
| CN107970768B (en) | Gas diffusion electrode and preparation method thereof and NOxConversion device | |
| CN107546038B (en) | A kind of concentration difference capacitor | |
| KR102244158B1 (en) | Electrochemical system for producing ammonium nitrate from nitrogen oxides and preparation method thereof | |
| US20230201764A1 (en) | Device and method based on electrically-driven chemical carbon pump combined cycle for diluted carbon source | |
| WO2023178913A1 (en) | Hydrogen impurity purification apparatus used for fuel cell | |
| KR102179532B1 (en) | An electrolytic apparatus for removing nitrogen oxides, and a method for removing nitrogen oxides | |
| KR102022447B1 (en) | Method of manufacturing high-purity of vanadium electrolyte for vanadium redox flow batteries by using catalytic reactor | |
| CN114515494B (en) | Direct air capture carbon dioxide energy saving system and method with precise ion control | |
| CN113789538B (en) | Gas diffusion cathode with suspension catalyst layer and electrochemical reactor | |
| CN115992360A (en) | Carbon dioxide treatment device and method, and method for producing carbon compound | |
| KR102383399B1 (en) | A simultaneous removal system of nitrogen oxides and sulfur oxides from flue gas and its method | |
| CN108404615A (en) | A kind of simultaneous removing sulphur nitrate for sulfuric acid and nitric acid method and device | |
| CN217114472U (en) | Hydrogen purification device for fuel cell | |
| US20230287581A1 (en) | Carbon dioxide treatment appratus, carbon dioxide treatment method, and method of producing ethylene | |
| CN204365126U (en) | The device of liquid phase purification industrial SO 2 waste gas is worked in coordination with in electrodialysis | |
| CN113120866B (en) | Method for preparing elemental sulfur by using sulfur dioxide | |
| KR102315001B1 (en) | Electrochemical Conversion System of NOx and NOx Conversion Method | |
| CN112725816B (en) | Method and device for preparing hydrogen sulfide by sulfur dioxide electrocatalytic reduction in cooperation with membrane separation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |