CN116732552A - Electrocatalytic nitrogen reduction ammonia synthesis reaction device, system and ammonia synthesis method - Google Patents
Electrocatalytic nitrogen reduction ammonia synthesis reaction device, system and ammonia synthesis method Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 261
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 197
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 127
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 96
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 51
- 238000001308 synthesis method Methods 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 136
- 239000007788 liquid Substances 0.000 claims abstract description 76
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000000926 separation method Methods 0.000 claims abstract description 50
- 238000009792 diffusion process Methods 0.000 claims abstract description 49
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 48
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 48
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims description 48
- 239000003054 catalyst Substances 0.000 claims description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 239000012528 membrane Substances 0.000 claims description 28
- 239000003792 electrolyte Substances 0.000 claims description 24
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- 238000006722 reduction reaction Methods 0.000 abstract description 63
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- 230000009286 beneficial effect Effects 0.000 abstract description 6
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- 229910052760 oxygen Inorganic materials 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 17
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- 229910001873 dinitrogen Inorganic materials 0.000 description 6
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- 229910001092 metal group alloy Inorganic materials 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910001182 Mo alloy Inorganic materials 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical group [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 3
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- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 150000001449 anionic compounds Chemical class 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001767 cationic compounds Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
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- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
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- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
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- 239000003337 fertilizer Substances 0.000 description 1
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- 239000003517 fume Substances 0.000 description 1
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- 239000003345 natural gas Substances 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/27—Ammonia
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
- C25B15/083—Separating products
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to an electrocatalytic nitrogen reduction synthesis ammonia reaction device, an electrocatalytic nitrogen reduction synthesis ammonia reaction system and an synthesis ammonia method, and belongs to the technical field of synthesis ammonia. The nitrogen inlet is arranged on the cathode cover plate, and the first liquid inlet and the cathode product outlet are arranged on the frame, so that nitrogen is preferentially diffused to the surface of the cathode gas diffusion electrode, and is not directly introduced into water; under the electrocatalytic effect, nitrogen and water undergo a reduction reaction under the electronic effect input by a power supply to generate ammonia, the generated ammonia is very easy to dissolve in water to form ammonia water, and the ammonia water is discharged from a cathode product outlet of the frame; the invention is beneficial to gas-liquid separation and concentration of ammonia water, and the ammonia water which is easy to store is obtained, nitrogen and water are used as raw materials, high-temperature and high-pressure reaction conditions are not needed, the reaction conditions are relatively mild, energy conservation and carbon emission are facilitated, dust and toxic and harmful gas can be avoided, and the invention has the advantages of high efficiency, cleanness and low cost.
Description
Technical Field
The invention relates to the technical field of synthetic ammonia, in particular to an electrocatalytic nitrogen reduction synthetic ammonia reaction device, an electrocatalytic nitrogen reduction synthetic ammonia reaction system and a synthetic ammonia method.
Background
Ammonia (NH) 3 ) Is an important chemical raw material and is mainly used in the fields of agricultural fertilizers, industrial products, civil chemicals and the like. Because ammonia can be condensed into colorless liquid ammonia by cooling to-33.4 ℃ under normal pressure, the storage and transportation of the liquid ammonia are convenient, and the volume energy density of the liquid ammonia is about 2 times that of liquid hydrogen, ammonia is also considered as a fuel and a hydrogen storage carrier with development potential in the future. At present, the Haber method is dominant in the industrial ammonia synthesis technology, the Haber method reaction is required to be carried out under the conditions of high temperature and high pressure, the temperature is required to reach 300-500 ℃, the pressure is required to reach 15-20 MPa, and the energy consumption is huge. The raw materials of the synthetic ammonia are nitrogen and hydrogen, the nitrogen is mainly obtained through air separation, the hydrogen is produced by coal hydrogen production, natural gas hydrogen production and other processes, a large amount of carbon dioxide can be discharged, dust, nitrogen/sulfur oxide and the like can be generated, and serious atmospheric pollution is caused. The electrocatalytic nitrogen reduction is a novel technology for synthesizing ammonia, the raw materials for reaction are nitrogen and water, green electric power generated by renewable energy sources such as solar energy, wind energy and the like is used as driving force to realize the reaction of synthesizing ammonia under normal temperature and normal pressure, and the process is clean and low in carbon and energy consumption, and has wide development prospect. At present, the research and development of catalysts and the design of reaction devices required for synthesizing ammonia by electrocatalytic nitrogen reduction are important points of research in the field.
The existing reaction device for synthesizing ammonia by electrocatalytic nitrogen reduction mainly comprises the following steps: (1) The back-to-back type electrocatalytic nitrogen reduction ammonia synthesis electrolyzer mainly comprises a porous anode, a porous cathode and a polymer membrane (proton exchange membrane) for separating the porous anode and the porous cathode; the vaporized water enters the porous anode and reaches the surface of the catalyst through the gas diffusion layer to perform oxidation reaction, and the generated oxygen flows out along with unreacted water vapor. The hydrogen protons are transmitted to the surface of the cathode catalyst through the exchange membrane and undergo a reduction reaction with nitrogen diffused from the porous cathode to generate ammonia; however, the vaporization of the reactant (water) entering the porous anode causes additional energy consumption, and has lower supply efficiency relative to liquid water, and the wettability of the proton exchange membrane is difficult to maintain, so that the hydrogen proton conductivity is reduced, and the efficiency of cathode ammonia synthesis is affected; the cathode product is gaseous ammonia, and the volume of the container required for collecting and storing is large. (2) An electrolytic tank for synthesizing ammonia by electrocatalytic nitrogen reduction of polymer electrolyte membrane type, wherein a polymer membrane (proton exchange membrane) separates an anode chamber from a cathode chamber, and a reduction catalyst is loaded on the polymer membrane; in the anode pool, a strong alkaline aqueous solution such as KOH is generally used as electrolyte, nitrogen is directly introduced into the cathode cavity, and the nitrogen passes through the gas diffusion layer to the surface of the reduction catalyst for carrying out synthetic ammonia reaction; the reduction product of the electrolytic tank is ammonia, the volume of a container required for collecting and storing is large, in addition, the back mixing phenomenon of the product (ammonia) and the reactant (nitrogen) in the cathode chamber is easy to occur, the reduction reaction of the nitrogen is blocked, and the ammonia synthesis efficiency is reduced; (3) An H-type electrocatalytic nitrogen reduction ammonia synthesis electrolytic tank (called an H-type electrolytic tank for short) is the most common electrocatalytic electrolytic tank, a cathode tank and an anode tank are separated by a proton exchange membrane, electrolyte of the two reaction tanks is the same alkaline electrolyte (aqueous solution such as KOH) and a catalyst is loaded on the surface of an electrode plate; in the cathode pool, nitrogen is introduced into water and diffuses to the surface of the catalyst on the electrode to react, so that ammonia gas is generated, and the ammonia gas has excellent water solubility (53.97 g/100g of water) and is directly dissolved in the solution. The chemical reaction of the surface of the reacted electrode is more severe, the electrode is not suitable for being used as a voltage reference, and the reference electrode can be used as a reference base for externally applied voltage driving force; however, the electrolytic tank needs to introduce nitrogen into the electrolyte solution of the cathode cell firstly and then diffuse the nitrogen to the surface of the catalyst of the electrode for reaction, and 1 volume of water can only dissolve 0.02 volume of nitrogen due to poor water solubility of the nitrogen, so that the efficiency of the reaction of synthesizing ammonia is greatly limited; (4) The electrolytic tank does not use a proton exchange membrane to separate a cathode reaction zone from an anode reaction zone, so that cross coupling reaction is easy to generate, anodic oxidation products are diffused to a cathode to generate reduction reaction, and cathodic reduction products are diffused to an anode to generate oxidation reaction.
Therefore, there is an urgent need in the art to develop an electrocatalytic nitrogen reduction ammonia synthesis reaction device and system for producing ammonia water easy to store, and improving the ammonia synthesis reaction efficiency.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an electrocatalytic nitrogen reduction ammonia synthesis reaction device, an electrocatalytic nitrogen reduction ammonia synthesis reaction system and an ammonia synthesis method which are used for producing ammonia water easy to store and high in ammonia synthesis efficiency.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides an electrocatalytic nitrogen reduction synthesis ammonia reaction device, which comprises a cathode reaction chamber and an anode reaction chamber, wherein a proton exchange membrane is arranged between the cathode reaction chamber and the anode reaction chamber, and the proton exchange membrane is attached to a sieve plate;
a cathode cover plate is arranged on one side, far away from the proton exchange membrane, of the cathode reaction chamber, a cathode gas diffusion electrode is arranged in the cathode reaction chamber, and a frame is arranged between the cathode gas diffusion electrode and the proton exchange membrane;
an anode electrode is arranged in the anode reaction chamber, and an anode cover plate is arranged on one side of the anode reaction chamber far away from the proton exchange membrane;
the cathode cover plate is fixedly connected with the frame, and the anode cover plate is fixedly connected with the frame; the cathode cover plate is provided with a nitrogen inlet, one side of the frame is provided with a cathode product outlet, the other side of the frame is provided with a first liquid inlet, and the anode cover plate is provided with an anode product outlet and a second liquid inlet.
The invention takes nitrogen and water (or electrolyte water solution) as raw materials, nitrogen is introduced into a cathode reaction chamber from a nitrogen inlet, and water respectively enters the cathode reaction chamber and an anode reaction chamber through a first liquid inlet and a second liquid inlet.
The nitrogen inlet is arranged on the cathode cover plate, and the first liquid inlet and the cathode product outlet are arranged on the frame, so that nitrogen is preferentially diffused to the surface of the cathode gas diffusion electrode, and is not directly introduced into water; under the electrocatalytic effect, nitrogen and water undergo a reduction reaction under the electronic effect input by a power supply to generate ammonia, the generated ammonia is very easy to dissolve in water to form ammonia water, and the ammonia water is discharged from a cathode product outlet of the frame; so as to obtain the ammonia water which is easy to store after gas-liquid separation and concentration of the ammonia water.
In the anode reaction chamber, the aqueous solution generates water oxidation reaction on the surface of the anode electrode to generate oxygen, and electrons generated in the reaction process are converged to a power supply through the electrode.
As a preferred embodiment of the present invention, a gap is left between the cathode gas diffusion electrode and the cathode cover plate; and a diversion trench is arranged on one side of the cathode cover plate, which is close to the cathode gas diffusion electrode.
Further, the distance between the cathode gas diffusion electrode and the cathode cover plate is 2-10 mm.
The space formed by the cathode gas diffusion electrode and the cathode cover plate can be used as a reactant (N 2 ) The diversion trench can form stable and uniform diffusion pressure of the nitrogen flowing to the diffusion electrode in the space.
As a preferred embodiment of the present invention, the cathode gas diffusion electrode includes a cathode gas diffusion layer, a cathode current collecting plate, and a cathode catalyst layer, which are sequentially disposed.
Further, the cathode gas diffusion layer is carbon fiber paper board, and the cathode current collecting plate is a copper net.
Further, the preparation method of the cathode catalyst layer comprises the following steps:
fully dispersing and mixing a cathode nitrogen reduction catalyst in a perfluorinated sulfonic acid polymer solution to obtain a mixed material; spraying the mixed material on a cathode current collecting plate, and forming a cathode catalyst layer on the cathode current collecting plate after drying treatment.
Further, the cathode nitrogen reduction catalyst is granular, and the average grain diameter is 50-3000 nm; the cathode nitrogen reduction catalyst comprises metal alloy particles and sulfur oxide particles, wherein the mass fraction of the metal alloy in the cathode nitrogen reduction catalyst is 80-95%, and the metal alloy comprises at least two of iron, molybdenum, tungsten, cobalt and manganese.
Further, the thickness of the cathode catalyst layer is 1 to 200 μm.
As a preferred embodiment of the invention, the thickness of the frame is 5-15 mm, so that a certain space is reserved between the proton exchange membrane and the cathode gas diffusion electrode for the reactant H 2 O, so that H 2 O participates in the reaction of nitrogen reduction to ammonia.
As a preferred embodiment of the present invention, the anode cover plate is provided with a groove at a side close to the anode electrode, and the anode electrode is disposed at a groove opening of the anode cover plate.
Further, the depth of the groove is 5-15 mm.
In the present invention, the grooves are designed as reactant H 2 O leaves a reaction space.
As a preferred embodiment of the present invention, the anode electrode is composed of nickel foam, and an anode catalyst layer supported on the surface of the nickel foam.
Further, the preparation method of the anode electrode comprises the following steps:
the electrochemical reduction deposition method loads a water oxidation catalyst on the foam nickel, and forms an anode catalyst layer on the foam nickel.
Further, the water oxidation catalyst is nickel-molybdenum alloy, and the molar ratio of nickel element to molybdenum element in the nickel-molybdenum alloy is Ni: mo= (0.5 to 10): 1.
further, the anode catalyst layer has a thickness of 5 to 500 μm.
As a preferred embodiment of the invention, the cathode gas diffusion electrode is in sealing fit with the cathode cover plate through a sealing ring, the frame is in sealing fit with the cathode gas diffusion electrode through a sealing ring, the frame is in sealing fit with the proton exchange membrane through a sealing ring, the sieve plate is in sealing fit with the anode cover plate through a sealing ring, the cathode cover plate is fixedly connected with the frame through bolts, and the anode cover plate is fixedly connected with the frame through bolts, so that the cathode cover plate, the cathode gas diffusion electrode, the frame, the proton exchange membrane, the sieve plate, the anode electrode and the anode cover plate are sequentially compressed to form a cathode reaction chamber and an anode reaction chamber.
In a second aspect, the invention provides an electrocatalytic nitrogen reduction synthesis ammonia reaction system, which comprises the electrocatalytic nitrogen reduction synthesis ammonia reaction device according to the first aspect; the cathode cover plate is characterized by further comprising an air separation device, a reverse osmosis device and an electrolyte water solution tank, wherein a nitrogen outlet of the air separation device is connected with a nitrogen inlet of the cathode cover plate through a pipeline, a water outlet of the reverse osmosis device is connected with the electrolyte water solution tank through a pipeline, and the electrolyte water solution tank is connected with a first liquid inlet and a second liquid inlet through pipelines respectively.
In the invention, the air separation device is used for separating nitrogen from air, the reverse osmosis device is used for preprocessing tap water to remove suspended matters, colloid and other impurities in the water, and an electrolyte such as potassium hydroxide is added into the electrolyte aqueous solution tank to prepare an alkaline electrolyte aqueous solution. And introducing nitrogen and electrolyte aqueous solution into the electrocatalytic nitrogen reduction ammonia synthesis reaction device, and electrifying to perform electrocatalytic nitrogen reduction ammonia synthesis reaction.
As a preferred embodiment of the invention, the electrocatalytic nitrogen reduction synthesis ammonia reaction system further comprises a first gas-liquid separation device and an ammonia water concentration device, wherein an inlet of the first gas-liquid separation device is connected with a cathode product outlet of the frame through a pipeline, a gas outlet of the first gas-liquid separation device is connected with a nitrogen inlet of the cathode cover plate through a pipeline, a liquid outlet of the first gas-liquid separation device is connected with an inlet of the ammonia water concentration device through a pipeline, and an aqueous solution outlet of the ammonia water concentration device is connected with a first liquid inlet of the frame through a pipeline.
The mixture discharged from the cathode reaction chamber enters the first gas-liquid separation device through a pipeline to carry out gas-liquid separation, nitrogen and ammonia water are separated, the separated nitrogen is input into the cathode reaction chamber again through a pipeline, ammonia water enters the ammonia water concentration device through a pipeline to concentrate, aqueous solution and concentrated ammonia water are separated, the aqueous solution separated by the ammonia water concentration device is input into the cathode reaction chamber again through a pipeline, and the concentrated ammonia water is input into the ammonia water storage tank through a pipeline to be stored.
As a preferred embodiment of the invention, the electrocatalytic nitrogen reduction synthesis ammonia reaction system further comprises a second gas-liquid separation device, wherein an inlet of the second gas-liquid separation device is connected with an anode product outlet of the anode cover plate through a pipeline, and an aqueous solution outlet of the second gas-liquid separation device is connected with a second liquid inlet of the anode cover plate through a pipeline.
The mixture discharged from the anode reaction chamber enters a second gas-liquid separation device through a pipeline to carry out gas-liquid separation, oxygen and aqueous solution are separated, the oxygen is input into an oxygen storage tank through a pipeline to be stored, and the aqueous solution is input into the anode reaction chamber again through the pipeline.
In a third aspect, the present invention provides a method for electrocatalytic nitrogen reduction synthesis ammonia, implemented by the electrocatalytic nitrogen reduction synthesis ammonia reaction system according to the second aspect, comprising the following steps:
introducing nitrogen into the cathode reaction chamber from the nitrogen inlet, adding an aqueous solution into the cathode reaction chamber through the first liquid inlet, adding an aqueous solution into the anode reaction chamber of the reaction device through the second liquid inlet, connecting the negative electrode of the power supply with the wiring end of the cathode gas diffusion electrode, and connecting the positive electrode of the power supply with the wiring end of the anode electrode.
Compared with the traditional Haber method ammonia synthesis process, the method takes nitrogen and water as raw materials, does not need high-temperature high-pressure reaction conditions, has relatively mild reaction conditions, is beneficial to energy conservation, has no carbon emission, can avoid dust and toxic and harmful gas, and has the advantages of high efficiency, cleanness and low cost.
As a preferred embodiment of the invention, in the process of synthesizing ammonia by electrocatalytic nitrogen reduction, the nitrogen pressure in the anode reaction chamber is 0.01-1.0 MPa, the aqueous solution is added into the cathode reaction chamber at a flow rate of 0.1-10L/min, and the aqueous solution is added into the cathode reaction chamber at a flow rate of 0.1-10L/min.
As a preferred embodiment of the present invention, the aqueous solution is an aqueous electrolyte solution including at least one of an aqueous potassium hydroxide solution and an aqueous sodium hydroxide solution, and the concentration of the aqueous electrolyte solution is 0.05 to 1.0mol/L. Compared with pure water, the electrolyte aqueous solution has better ion conduction capability, and is beneficial to improving the efficiency of electrocatalytic synthesis of ammonia.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the nitrogen inlet is arranged on the cathode cover plate, the first liquid inlet and the cathode product outlet are arranged on the frame, so that nitrogen is not directly introduced into water, the nitrogen is firstly diffused to the surface of the cathode gas diffusion electrode, under the electrocatalytic effect, the nitrogen and the water undergo a reduction reaction under the electronic effect input by the power supply to generate ammonia, the generated ammonia is very easy to dissolve in the water to form ammonia water, and the ammonia water is discharged from the cathode product outlet of the frame; so as to obtain ammonia water which is easy to store through gas-liquid separation and concentration of the ammonia water;
(2) The invention uses nitrogen and water as raw materials, does not need high-temperature high-pressure reaction conditions, has relatively mild reaction conditions, is beneficial to saving energy sources, has no carbon emission, can avoid dust and toxic and harmful gas, and has the advantages of high efficiency, cleanness and low cost.
Drawings
FIG. 1 is an exploded schematic view of an electrocatalytic nitrogen reduction ammonia synthesis reaction apparatus according to example 1 of the present invention;
FIG. 2 is a schematic diagram of electrocatalytic reduction of nitrogen synthesis ammonia as provided in example 1 of the present invention;
FIG. 3 is a schematic diagram of the system for electrocatalytic nitrogen reduction synthesis ammonia reaction provided in example 2 of the present invention.
In the figure, the 100-electrocatalytic nitrogen reduction synthesis ammonia reaction device, 110-proton exchange membrane, 120-cathode gas diffusion electrode, 121-cathode gas diffusion layer, 122-cathode current collecting plate, 123-cathode catalyst layer, 130-cathode cover plate, 131-nitrogen inlet, 140-frame, 141-cathode product outlet, 142-first liquid inlet, 150-anode cover plate, 151-anode product outlet, 152-second liquid inlet, 160-screen plate, 170-anode electrode, 180-sealing ring, 200-air separation device, 300-reverse osmosis device, 400-electrolyte water solution tank, 500-first gas-liquid separation device, 600-ammonia concentration device, 700-ammonia water storage tank, 800-second gas-liquid separation device and 900-oxygen storage tank.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
Example 1
The embodiment provides an electrocatalytic nitrogen reduction ammonia synthesis reaction device, and please refer to fig. 1.
The electrocatalytic nitrogen reduction ammonia synthesis reaction device 100 comprises a cathode reaction chamber and an anode reaction chamber, wherein a proton exchange membrane 110 is arranged between the cathode reaction chamber and the anode reaction chamber.
A cathode gas diffusion electrode 120 is disposed in the cathode reaction chamber, a cathode cover plate 130 is disposed on one side of the cathode reaction chamber far away from the proton exchange membrane 110, and the cathode gas diffusion electrode 120 includes a cathode gas diffusion layer 121, a cathode current collecting plate 122 and a cathode catalyst layer 123 which are sequentially disposed; the cathode current collecting plate 122 is a metal mesh structure, such as a copper mesh, for functioning as a current collector, and collecting current during the reaction; the cathode catalyst layer 123 is coated on the surface of the cathode current collecting plate 122, and the thickness of the cathode catalyst layer 123 is 1-200 mu m; the cathode current collecting plate 122 is attached to the cathode gas diffusion layer 121 covered with the cathode catalyst layer 123 to form a cathode gas diffusion electrode 120; a gap is reserved between the cathode gas diffusion electrode 120 and the cathode cover plate 130, the distance between the cathode gas diffusion electrode 120 and the cathode cover plate 130 is 2-10 mm, the cathode cover plate 130 is made of polytetrafluoroethylene, and a diversion trench is arranged on one side of the cathode cover plate 130 close to the cathode gas diffusion electrode 120. Is formed by a cathode gas diffusion electrode 120 and a cathode cover plate 130The resulting space can be used as a reactant (N 2 ) The flow guiding groove is arranged, so that the nitrogen can form stable and uniform diffusion pressure flowing to the diffusion electrode in the space.
A method of preparing the cathode catalyst layer 123, comprising the steps of:
fully dispersing and mixing a cathode nitrogen reduction catalyst in a perfluorinated sulfonic acid polymer solution to obtain a mixed material; the cathode nitrogen reduction catalyst is granular, the average grain diameter is 50-3000 nm, the cathode nitrogen reduction catalyst comprises metal alloy grains and sulfur oxide grains, the mass fraction of the metal alloy in the cathode nitrogen reduction catalyst is 80-95%, and the metal alloy comprises at least two of iron, molybdenum, tungsten, cobalt and manganese; the mixture is sprayed on the cathode current collecting plate 122 and dried at 60-300 c, thereby forming the cathode catalyst layer 123 on the cathode current collecting plate 122.
A frame 140 is arranged between the proton exchange membrane 110 and the cathode gas diffusion electrode 120, and the thickness of the frame 140 is 5-15 mm, so that a certain space is reserved between the proton exchange membrane 110 and the cathode gas diffusion electrode 120, and the reserved space can be used for a reactant H 2 Reaction space of O so as to H 2 O participates in the reaction of nitrogen reduction to ammonia.
The anode reaction chamber is provided with an anode cover plate 150 at one side far away from the proton exchange membrane 110, a sieve plate 160 and an anode electrode 170 are arranged in the anode reaction chamber, and the proton exchange membrane 110 is arranged on one side surface of the sieve plate 160 close to the cathode reaction chamber; the anode cover plate 150 is provided with a groove at one side close to the anode reaction chamber, the anode electrode 170 is arranged at the opening of the groove of the anode cover plate 150, and a gap is reserved between the anode electrode 170 and the bottom of the groove of the anode cover plate 150, so that a reactant H is obtained 2 The O leaves a reaction space, and the depth of the groove of the anode cover plate 150 is 5-15 mm.
The anode electrode 170 is composed of nickel foam and an anode catalyst layer supported on the surface of the nickel foam, the thickness of the anode catalyst layer is 5-500 μm, and the anode catalyst layer is positioned on the surface of one side of the nickel foam, which is far away from the anode cover plate 150.
The preparation method of the anode electrode 170 comprises the following steps:
loading a water oxidation catalyst on the foam nickel by adopting an electrochemical reduction deposition method, so as to form an anode catalyst layer on the foam nickel; the water oxidation catalyst is nickel-molybdenum alloy, and the molar ratio of nickel element to molybdenum element in the nickel-molybdenum alloy is Ni: mo= (0.5 to 10): 1.
in this embodiment, the cathode gas diffusion electrode 120 is in sealing fit with the cathode cover plate 130 through a sealing ring 180, the frame 140 is in sealing fit with the cathode gas diffusion electrode 120 through a sealing ring 180, the frame 140 is in sealing fit with the proton exchange membrane 110 through a sealing ring 180, the screen plate 160 is in sealing fit with the anode cover plate 150 through a sealing ring 180, the cathode cover plate 130 is fixedly connected with the frame 140 through bolts, and the anode cover plate 150 is fixedly connected with the frame 140 through bolts, so that the cathode cover plate 130, the cathode gas diffusion electrode 120, the frame 140, the proton exchange membrane 110, the screen plate 160, the anode electrode 170 and the anode cover plate 150 are sequentially compressed to form a cathode reaction chamber and an anode reaction chamber.
In this embodiment, the cathode cover 130 is provided with a nitrogen inlet 131, one side of the frame 140 is provided with a cathode product outlet 141, the other side of the frame 140 is provided with a first liquid inlet 142, and the anode cover 150 is provided with an anode product outlet 151 and a second liquid inlet 152.
In this example, the overall reaction of electrocatalytic nitrogen reduction to ammonia is: n (N) 2 +3H 2 O→2NH 3 +1.5O 2 . As shown in fig. 1 to 2, the electrocatalytic nitrogen reduction ammonia synthesis reaction apparatus 100 operates as follows:
introducing nitrogen gas into the cathode reaction chamber from the nitrogen gas inlet 131, introducing an aqueous solution into the cathode reaction chamber from the first liquid inlet 141, and introducing an aqueous solution into the anode reaction chamber from the second solution inlet 152; connecting the negative electrode of the power supply with the wiring end of the cathode current collecting plate 122 through a wire, and connecting the positive electrode of the power supply with the wiring end of the electrode through a wire;
in the cathode reaction chamber, nitrogen gas permeates the cathode gas diffusion layer 121, and the surface of the cathode catalyst layer 123 on the cathode current collecting plate 122 is connected with water and electrons input by a power supplyThe reduction reaction is carried out to generate ammonia, and the reaction formula is as follows: n (N) 2 +6H 2 O+6e - →2NH 3 +6OH - ；
In the anode reaction chamber, the aqueous solution undergoes a water oxidation reaction on the surface of the anode electrode 170 to generate oxygen, and electrons generated in the reaction process are converged to a power supply through the electrode, wherein the reaction formula is as follows: 6OH - →1.5O 2 +6e - +3H 2 O。
Example 2
The embodiment provides an electrocatalytic nitrogen reduction ammonia synthesis reaction system, which comprises the electrocatalytic nitrogen reduction ammonia synthesis reaction device 100 of embodiment 1, and further comprises: an air separation device 200, a reverse osmosis device 300, an electrolyte water solution tank 400, a first gas-liquid separation device 500, an ammonia concentration device 600, an ammonia storage tank 700, a second gas-liquid separation device 800 and an oxygen storage tank 900; wherein, the nitrogen outlet of the air separation unit 200 is connected with the nitrogen inlet 131 of the cathode cover plate 130; the water outlet of the reverse osmosis device 300 is connected with the electrolyte water solution tank 400 through a pipeline, and the electrolyte water solution tank 400 is connected with the first liquid inlet 142 and the second liquid inlet 152 through pipelines respectively; the inlet of the first gas-liquid separation device 500 is connected with the cathode product outlet 141 of the frame 140 through a pipeline, the gas outlet of the first gas-liquid separation device 500 is connected with the nitrogen inlet 131 of the cathode cover plate 130 through a pipeline, the liquid outlet of the first gas-liquid separation device 500 is connected with the inlet of the ammonia water concentration device 600 through a pipeline, the aqueous solution outlet of the ammonia water concentration device 600 is connected with the first liquid inlet 142 of the frame 140 through a pipeline, and the ammonia water outlet of the ammonia water concentration device 600 is connected with the inlet of the ammonia water storage tank 700 through a pipeline; the inlet of the second gas-liquid separation device 800 is connected with the anode product outlet 151 of the anode cover plate 150 through a pipe, the gas outlet of the second gas-liquid separation device 800 is connected with the inlet of the oxygen storage tank 900 through a pipe, and the aqueous solution outlet of the second gas-liquid separation device 800 is connected with the second liquid inlet 152 of the anode cover plate 150 through a pipe.
Flow control valves are respectively arranged on the pipelines of the embodiment.
In the embodiment, the reverse osmosis device 300 is used for preprocessing tap water to remove suspended matters, colloid, inorganic cations, inorganic anions and other impurities in the tap water, and the preprocessed water enters an electrolyte water solution tank through a pipeline to dissolve potassium hydroxide in water to prepare potassium hydroxide solution serving as an electrolyte water solution; the electrolyte aqueous solution has better ion conduction capability than pure water, and is beneficial to improving the efficiency of electrocatalytic synthesis of ammonia.
The mixture discharged from the cathode reaction chamber enters the first gas-liquid separation device 500 through a pipeline for gas-liquid separation, nitrogen and ammonia water are separated, the separated nitrogen is input into the cathode reaction chamber again through a pipeline, ammonia water enters the ammonia water concentration device 600 through a pipeline for concentration, aqueous solution and concentrated ammonia water are separated, the aqueous solution separated by the ammonia water concentration device 600 is input into the cathode reaction chamber again through a pipeline, and the concentrated ammonia water is input into the ammonia water storage tank 700 through a pipeline for storage.
The mixture discharged from the anode reaction chamber is introduced into the second gas-liquid separation device 800 through a pipe to perform gas-liquid separation, oxygen and an aqueous solution are separated, the oxygen is introduced into the oxygen storage tank 900 through a pipe to be stored, and the aqueous solution is introduced into the anode reaction chamber again through a pipe.
Examples 3 to 11
Examples 3 to 11 respectively provide an electrocatalytic nitrogen reduction synthesis ammonia process, which is carried out by an electrocatalytic nitrogen reduction synthesis ammonia reaction system, and examples 3 to 11 differ from example 2 in that: the cathode current collecting plate 122 is a copper net, the cathode gas diffusion layer 121 is a carbon fiber paperboard, the cathode nitrogen reduction catalyst used by the cathode catalyst layer 123 is nano Fe-Ni-Co alloy powder (from Shanghai Ala Biochemical technology Co., ltd., product number is F140003); the water oxidation catalyst used in the anode catalyst layer is Raney nickel (CAS number 7440-02-0, available from Shanghai Ala Biochemical technologies Co., ltd.); the thicknesses of the cathode catalyst layer 123 and the anode catalyst layer are shown in table 1.
The electrocatalytic nitrogen reduction ammonia synthesis method comprises the following steps:
(1) Introducing tap water into the reverse osmosis device 300 for pretreatment to remove suspended matters, colloid, inorganic cations, inorganic anions and other impurities in the tap water, introducing the pretreated water into an electrolyte aqueous solution tank 400 through a pipeline, dissolving potassium hydroxide into the water to prepare a potassium hydroxide aqueous solution, and taking the potassium hydroxide aqueous solution as the electrolyte aqueous solution, wherein the concentration is shown in table 1;
(2) Introducing nitrogen gas into the cathode reaction chamber from a nitrogen gas inlet 131; introducing an aqueous electrolyte solution into the cathode reaction chamber from the first liquid inlet 141 and an aqueous electrolyte solution into the anode reaction chamber from the second liquid inlet 152;
connecting the negative electrode of the power supply with the wiring end of the cathode current collecting plate 122 through a wire, and connecting the positive electrode of the power supply with the wiring end of the electrode through a wire;
in the cathode reaction chamber, nitrogen permeates the cathode gas diffusion layer 121, the surface of the cathode catalyst layer 123 on the cathode current collecting plate 122 undergoes a reduction reaction with water and electrons input by a power supply to generate ammonia gas, the ammonia gas is rapidly dissolved into ammonia water in an aqueous solution, and the ammonia water and part of unreacted nitrogen gas flow out of the cathode reaction chamber;
in the anode reaction chamber, the aqueous solution generates water oxidation reaction on the surface of the anode electrode 170 to generate oxygen, electrons generated in the reaction process are converged to a power supply through the electrode, and the oxygen and the aqueous solution flow out of the anode reaction chamber together;
the mixture discharged from the cathode reaction chamber enters the first gas-liquid separation device 500 through a pipeline for gas-liquid separation, nitrogen and ammonia water are separated, the separated nitrogen is re-input into the cathode reaction chamber through a pipeline, the ammonia water enters the ammonia water concentration device 600 through a pipeline for concentration, the aqueous solution and the concentrated ammonia water are separated, the aqueous solution separated by the ammonia water concentration device 600 is re-input into the cathode reaction chamber through a pipeline, and the concentrated ammonia water is input into the ammonia water storage tank 700 through a pipeline for storage;
the mixture discharged from the anode reaction chamber is introduced into the second gas-liquid separation device 800 through a pipe to perform gas-liquid separation, oxygen and an aqueous solution are separated, the oxygen is introduced into the oxygen storage tank 900 through a pipe to be stored, and the aqueous solution is introduced into the anode reaction chamber again through a pipe.
In the step (2), in the cathode reaction chamber, the pressure of the nitrogen and the inflow rate of the aqueous solution can be adjusted according to the actual reaction requirement, and the cathode reaction product is mixed with the unreacted nitrogen and the aqueous solution to flow out. After the subsequent separation process, the unreacted nitrogen and the water solution are separated again and are continuously put into a reaction device to participate in the reaction; in the anode reaction chamber, the anode reaction product is mixed with the unreacted aqueous solution to flow out. And (3) through the subsequent separation process, the unreacted aqueous solution is separated again and is continuously put into a reaction device to participate in the reaction.
The core device for the single-pass conversion rate test of the synthetic ammonia is a gas chromatograph, and the specific test operation steps are as follows:
(1) The method comprises the steps of completing the raw material gas (nitrogen), electrolyte solution and electric power access of the electrocatalytic nitrogen reduction synthesis ammonia reaction device, connecting a cathode product (ammonia) outlet channel with a gas chromatograph, and discharging an anode product (oxygen) outlet into a fume hood;
(2) After the raw material gas (nitrogen) and electrolyte solution are stabilized according to set parameters, such as pressure, flow and the like, the power supply is connected to start the catalytic synthesis ammonia reaction;
(3) After the reaction starts for half an hour, intercepting the mixed gas of the synthetic ammonia product in a certain period of time when the synthetic ammonia reaction reaches a steady state stage, and then analyzing the mixed gas by a gas chromatograph to further calculate the single pass conversion rate of the synthetic ammonia;
(4) In order to ensure certain reliability of the test result, the product analysis times are 5 times under each set of parameter conditions, and the test of each set of parameter conditions is repeated 3 times, so that the result is determined according to the average value of 15 times.
TABLE 1
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The electrocatalytic nitrogen reduction synthesis ammonia reaction device is characterized by comprising a cathode reaction chamber and an anode reaction chamber, wherein a proton exchange membrane is arranged between the cathode reaction chamber and the anode reaction chamber and is attached to a sieve plate;
a cathode cover plate is arranged on one side, far away from the proton exchange membrane, of the cathode reaction chamber, a cathode gas diffusion electrode is arranged in the cathode reaction chamber, and a frame is arranged between the cathode gas diffusion electrode and the proton exchange membrane;
an anode electrode is arranged in the anode reaction chamber, and an anode cover plate is arranged on one side of the anode reaction chamber far away from the proton exchange membrane;
the cathode cover plate is fixedly connected with the frame, and the anode cover plate is fixedly connected with the frame; the cathode cover plate is provided with a nitrogen inlet, one side of the frame is provided with a cathode product outlet, the other side of the frame is provided with a first liquid inlet, and the anode cover plate is provided with an anode product outlet and a second liquid inlet.
2. The electrocatalytic nitrogen reduction synthesis ammonia reaction device as claimed in claim 1, wherein a gap is left between the cathode gas diffusion electrode and the cathode cover plate; and a diversion trench is arranged on one side of the cathode cover plate, which is close to the cathode gas diffusion electrode.
3. The apparatus for electrocatalytic nitrogen reduction synthesis ammonia as defined in claim 1, wherein the cathode gas diffusion electrode comprises a cathode gas diffusion layer, a cathode current collector and a cathode catalyst layer arranged in sequence.
4. The electrocatalytic nitrogen reduction ammonia synthesis reaction device as claimed in claim 1, wherein the anode cover plate is provided with a groove at one side close to the anode electrode, and the anode electrode is arranged at the opening of the groove of the anode cover plate.
5. The electrocatalytic nitrogen reduction ammonia synthesis reaction device as claimed in claim 1, wherein the anode electrode is composed of foam nickel and an anode catalyst layer supported on the surface of the foam nickel.
6. An electrocatalytic nitrogen reduction synthesis ammonia reaction system, characterized by comprising an electrocatalytic nitrogen reduction synthesis ammonia reaction device according to any one of claims 1-5; the cathode cover plate is characterized by further comprising an air separation device, a reverse osmosis device and an electrolyte water solution tank, wherein a nitrogen outlet of the air separation device is connected with a nitrogen inlet of the cathode cover plate through a pipeline, a water outlet of the reverse osmosis device is connected with the electrolyte water solution tank through a pipeline, and the electrolyte water solution tank is connected with a first liquid inlet and a second liquid inlet through pipelines respectively.
7. The electrocatalytic nitrogen reduction synthesis ammonia reaction system of claim 6, further comprising a first gas-liquid separation device and an ammonia water concentration device, wherein an inlet of the first gas-liquid separation device is connected with a cathode product outlet of the frame through a pipeline, a gas outlet of the first gas-liquid separation device is connected with a nitrogen inlet of the cathode cover plate through a pipeline, a liquid outlet of the first gas-liquid separation device is connected with an inlet of the ammonia water concentration device through a pipeline, and an aqueous solution outlet of the ammonia water concentration device is connected with a first liquid inlet of the frame through a pipeline.
8. The electrocatalytic nitrogen reduction synthesis ammonia reaction system of claim 6, further comprising a second gas-liquid separation device, wherein an inlet of the second gas-liquid separation device is connected to an anode product outlet of the anode cover plate via a conduit, and an aqueous solution outlet of the second gas-liquid separation device is connected to a second liquid inlet of the anode cover plate via a conduit.
9. An electrocatalytic nitrogen reduction ammonia synthesis process carried out by an electrocatalytic nitrogen reduction ammonia synthesis reaction system as claimed in any one of claims 6 to 8, comprising the steps of:
introducing nitrogen into the cathode reaction chamber from the nitrogen inlet, adding an aqueous solution into the cathode reaction chamber through the first liquid inlet, adding an aqueous solution into the anode reaction chamber of the reaction device through the second liquid inlet, connecting the negative electrode of the power supply with the wiring end of the cathode gas diffusion electrode, and connecting the positive electrode of the power supply with the wiring end of the anode electrode.
10. The method for synthesizing ammonia by electrocatalytic nitrogen reduction according to claim 9, wherein the nitrogen pressure in the anode reaction chamber is 0.01-1.0 MPa and the aqueous solution is added into the cathode reaction chamber at a flow rate of 0.1-10L/min during the electrocatalytic nitrogen reduction to synthesize ammonia.
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