CN114959746A - System for synthesizing ammonia based on electrochemical principle - Google Patents
System for synthesizing ammonia based on electrochemical principle Download PDFInfo
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- CN114959746A CN114959746A CN202110928699.8A CN202110928699A CN114959746A CN 114959746 A CN114959746 A CN 114959746A CN 202110928699 A CN202110928699 A CN 202110928699A CN 114959746 A CN114959746 A CN 114959746A
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- 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
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- 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
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a system for synthesizing ammonia based on an electrochemical principle, which comprises a hydrogen supply tank, a synthetic ammonia reactor, a nitrogen supply tank and an ammonia treatment device, wherein the hydrogen supply tank is connected with the ammonia treatment device; the synthetic ammonia reactor comprises a membrane electrode assembly, an anode gas chamber and a cathode gas chamber; a humidifying component is communicated with the hydrogen supply tank and is communicated with the anode gas chamber; the nitrogen supply tank is communicated with the cathode gas chamber; the ammonia treatment device comprises an ammonia storage tank, and the ammonia storage tank is communicated with the cathode gas chamber; the anode gas chamber is also provided with a hydrogen discharge port. The synthesis ammonia reactor is electrified, hydrogen is dissociated into hydrogen protons in the anode gas chamber, nitrogen is subjected to reduction reaction in the cathode gas chamber and is combined with the hydrogen protons to generate ammonia, ammonia production based on the electrochemical principle is realized, the whole device is simple and easy to produce, the application scene is wide, energy consumption in the traditional ammonia production process is reduced to a great extent, ammonia is indirectly used as a hydrogen carrier, hydrogen energy can be conveniently utilized in the follow-up process no matter in transportation or storage, and a new idea is provided for the wide application of the hydrogen energy.
Description
Technical Field
The invention relates to the technical field of hydrogen storage, in particular to a system for synthesizing ammonia based on an electrochemical principle.
Background
The hydrogen energy has the characteristics of high heat value and environmental protection, and is a new energy with higher application prospect.
In the traditional hydrogen storage mode, hydrogen is generally stored in a hydrogen storage tank by a compression method, and the hydrogen storage tank needs to be designed to ensure the highest pressure of 98MPa during production in order to meet the requirement of hydrogen storage, and due to the existence of the hydrogen embrittlement phenomenon, the hydrogen storage tank has a nearly harsh condition in both material selection and process, so that the design difficulty of the hydrogen storage tank is increased to a great extent; meanwhile, the hydrogen energy is a troublesome problem in storage, transportation and utilization because the hydrogen storage tank is heavy.
Ammonia (NH) 3 ) The ammonia hydrogen storage carrier is a chemical raw material, wherein the mass fraction of hydrogen is 17.6%, the energy density can reach 300Wh/kg at most, and the hydrogen storage density of liquid ammonia is five times of that of a hydrogen storage tank under 35MPa, so that the ammonia can be stored in a liquid state at room temperature and about 0.8MPa, the ammonia is very suitable for long-distance transportation, and meanwhile, the ammonia has pungent smell, if leakage exists, the leakage can be found at the first time, the larger leakage loss is avoided, and the ammonia hydrogen storage carrier is a very good hydrogen storage carrier.
The nitrogen and the hydrogen can be used for synthesizing ammonia, namely, the hydrogen can be stored in ammonia gas in a mode of synthesizing ammonia, the ammonia synthesis in industry is realized by catalytically synthesizing N2 and H2 under the conditions of high temperature and high pressure, and the process has strict required conditions and extremely high energy consumption.
Disclosure of Invention
The invention aims to provide a system for synthesizing ammonia based on an electrochemical principle, which solves the problems of high synthesis requirement and high energy consumption in the traditional ammonia synthesis process, thereby facilitating the realization of the storage and utilization of hydrogen.
In order to achieve the purpose, the invention adopts the following technical scheme:
a system for synthesizing ammonia based on electrochemical principle comprises a hydrogen supply tank, a synthetic ammonia reactor, a nitrogen supply tank and an ammonia processing device; the synthetic ammonia reactor comprises a membrane electrode assembly, an anode gas chamber and a cathode gas chamber; a humidifying component is communicated with the hydrogen supply tank and is communicated with the anode gas chamber; the nitrogen supply tank is communicated with the cathode gas chamber; the ammonia treatment device comprises an ammonia storage tank, and the ammonia storage tank is communicated with the cathode gas chamber; and the anode gas chamber is also provided with a hydrogen discharge port.
Further preferably, the humidifying component is a humidifier; a hydrogen gas exhaust valve for exhausting redundant hydrogen gas is communicated with the humidifier; the system also comprises a first water tank which is communicated with the hydrogen discharging port; the first water tank is communicated with the humidifier so that the unreacted hydrogen in the synthesis ammonia reactor can flow back to the humidifier again.
Preferably, the humidifying component is a second water tank, and a spraying and bubbling component is arranged on the second water tank; and the hydrogen discharge port is communicated with a hydrogen discharge valve for discharging redundant hydrogen.
Further preferably, the membrane electrode assembly comprises an anode catalyst, a cathode catalyst and a proton conducting membrane; the anode catalyst and the cathode catalyst are respectively coated on two sides of the proton conducting membrane; the anode catalyst is a platinum-based catalyst; the cathode catalyst is a gold-based catalyst.
Further preferably, a hydrogen control valve is communicated between the hydrogen supply tank and the humidifying component; and a nitrogen control valve is communicated between the nitrogen supply tank and the synthesis reactor.
Further preferably, the ammonia treatment device further comprises a nitrogen separation device and a drying device; the nitrogen separation device and the drying device are arranged on a pipeline communicated with the cathode gas chamber and the ammonia storage tank in front and back.
Further preferably, the nitrogen separation device is a nitrogen separation tower; the drying device is a drying channel provided with calcium oxide.
Preferably, a first ammonia control valve is arranged on a pipeline between the cathode gas chamber and the nitrogen separation tower; an emptying valve for discharging nitrogen is arranged on the nitrogen separation tower; and a second ammonia control valve is arranged on a pipeline communicated between the drying channel and the ammonia storage tank.
The invention has the beneficial effects that:
a system for synthesizing ammonia based on electrochemical principle comprises a hydrogen supply tank, a synthetic ammonia reactor, a nitrogen supply tank and an ammonia processing device; the synthetic ammonia reactor comprises a membrane electrode assembly, an anode gas chamber and a cathode gas chamber; a humidifying component is communicated with the hydrogen supply tank and is communicated with the anode gas chamber; the nitrogen supply tank is communicated with the cathode gas chamber; the ammonia treatment device comprises an ammonia storage tank which is communicated with the cathode gas chamber. Under the condition of electrifying, hydrogen is dissociated into hydrogen protons in the anode gas chamber, nitrogen is combined with the hydrogen protons to generate ammonia after reduction reaction occurs in the cathode gas chamber, ammonia production based on the electrochemical principle is realized, the whole device is simple and easy to produce, the application scene is wide, the energy consumption in the traditional ammonia production process is reduced to a great extent, ammonia is indirectly used as a carrier of hydrogen, the hydrogen energy can be conveniently utilized in the follow-up process whether in transportation or storage, and a new idea is provided for the wide application of the hydrogen energy.
Drawings
FIG. 1 is a schematic view of the structure of a corresponding apparatus in example 1 of the present invention;
fig. 2 is a schematic structural diagram of a device corresponding to embodiment 2 of the present invention.
Names corresponding to the marks in the figure:
1. the device comprises a synthetic ammonia reactor, 12, a hydrogen discharge pipeline, 13, a first ammonia control valve, 2, a hydrogen supply tank, 20, a hydrogen control valve, 3, a nitrogen supply tank, 30, a nitrogen control valve, 4, an ammonia storage tank, 40, a second control valve, 5, a humidifier, 50, a hydrogen exhaust valve, 6, a nitrogen separation tower, 60, a nitrogen exhaust valve, 7, a first water tank, 8 and a second water tank.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below.
Example 1 of the invention:
as shown in fig. 1, a system for synthesizing ammonia based on electrochemical principle comprises a hydrogen supply tank 2, a synthetic ammonia reactor 1, a nitrogen supply tank 3 and an ammonia storage tank 4.
The synthetic ammonia reactor 1 comprises a membrane electrode assembly, an anode gas chamber and a cathode gas chamber; the membrane electrode assembly comprises an anode catalyst, a cathode catalyst and a proton conducting membrane; the membrane electrode assembly is positioned between the anode gas chamber and the cathode gas chamber; the anode gas chamber and the cathode gas chamber are respectively and correspondingly connected with an anode (anode) and a cathode (cathode) which are used for being connected with a power supply; the anode catalyst is a platinum-based catalyst, and the cathode catalyst is a gold-based catalyst.
Flow fields are arranged on the anode gas chamber and the cathode gas chamber to increase the circulation of hydrogen and nitrogen and further improve the efficiency of transfer and diffusion; diffusion layers are arranged between the anode gas chamber and the anode catalyst and between the cathode gas chamber and the cathode catalyst, and the diffusion layers are of porous structures, so that gas circulation is guaranteed, and meanwhile normal transfer of electrons is effectively guaranteed.
The hydrogen supply tank 2 is communicated with the anode gas chamber and is used for supplying hydrogen to the synthetic ammonia reactor 1; the nitrogen supply tank 3 is communicated with the cathode gas chamber and is used for supplying nitrogen to the synthetic ammonia reactor 1; the ammonia storage tank 4 is communicated with the cathode gas chamber of the synthetic ammonia reactor 1 and is used for storing the ammonia generated in the synthetic ammonia reactor 1.
A humidifier 5 is arranged on a pipeline communicated between the hydrogen supply tank 2 and the synthetic ammonia reactor 1 and is used for humidifying the hydrogen; a nitrogen separation tower 6 and a drying passage are arranged on a pipeline between the synthetic ammonia reactor 1 and the ammonia storage tank 4, the nitrogen separation tower 6 is used for separating nitrogen in the generated ammonia, and calcium oxide is arranged in the drying passage and is used for drying the discharged ammonia. In other embodiments, membrane humidification, an ejector or a hydrogen circulator can be used to humidify the hydrogen; the drying method can also adopt distillation, adsorption mode or other drying agents for drying.
In this example, the proton conducting membrane is a Nafion115 proton conducting membrane.
The system for synthesizing ammonia further comprises a first water tank 7, wherein the first water tank 7 is communicated with an anode gas chamber of the synthetic ammonia reactor 1 and is also communicated with the humidifier 5, unreacted hydrogen in the anode gas chamber flows into the first water tank 7 through a hydrogen discharge pipeline 12 communicated with a hydrogen discharge port arranged on the anode gas chamber to form saturated hydrogen rich in water, and then the saturated hydrogen enters the humidifier 5 to humidify fresh hydrogen coming from the hydrogen supply tank 2.
A hydrogen control valve 20 is arranged between the hydrogen supply tank 2 and the humidifier 5, and the hydrogen control valve 20 can control the pressure and the flow of the supplied hydrogen; the humidifier 5 is also provided with a pipeline communicated with the hydrogen collecting container, the pipeline is provided with a hydrogen emptying valve 50, after the hydrogen returns through the first water tank 7 and fresh hydrogen is humidified by the humidifier, redundant hydrogen enters the hydrogen collecting container through the pipeline provided with the hydrogen emptying valve 50. In other embodiments, the hydrogen gas may also be purged directly.
A nitrogen control valve 30 is also communicated on a pipeline between the nitrogen supply tank 3 and the synthetic ammonia reactor 1, and the nitrogen control valve 30 can control the pressure and the flow of the nitrogen introduced into the synthetic ammonia reactor 1; a first ammonia control valve 13 is arranged on a pipeline between the synthetic ammonia reactor 1 and the nitrogen separation tower 6, and is mainly used for controlling the flow and pressure of the discharged ammonia so as to fully ensure that the subsequent nitrogen separation step and the ammonia drying step are effectively carried out; the nitrogen separation tower 6 is provided with a pipeline connected with an external nitrogen collection container, the pipeline is provided with a nitrogen emptying valve 60, nitrogen separated from the nitrogen separation tower 6 enters the nitrogen collection container from the pipeline, and the collected nitrogen can be reused.
The working principle is as follows:
hydrogen in the hydrogen supply tank 2 enters the humidifier 5 through a hydrogen control valve 20, the humidified hydrogen enters an anode gas chamber, hydrogen protons are formed under the catalysis of power-on and platinum-based catalysts, and the hydrogen protons pass through a Nafion115 proton conduction membrane and enter the cathode side; the nitrogen in the nitrogen supply tank 3 enters the cathode gas chamber through the nitrogen control valve 30, and is subjected to reduction reaction under the action of power-on and gold-based catalysts and combined with hydrogen protons passing through the Nafion115 proton conduction membrane to generate ammonia. In the process, the pressure in the cathode gas chamber is controlled to be 1.5MPa, and the generated pressure can directly compress the generated ammonia into liquid ammonia. The liquid ammonia enters the nitrogen separation tower 6 after passing through the first ammonia control valve 13, wherein nitrogen contained in the liquid ammonia is separated in the nitrogen separation tower 6 and is discharged or collected for reuse through a pipeline provided with a nitrogen evacuation valve 60. The liquid ammonia after nitrogen removal continuously flows in the pipeline, and then is dried under the action of calcium oxide, and finally enters the ammonia storage tank 4 through the second ammonia control valve 40.
In the process, unreacted hydrogen in the anode gas chamber is discharged from the hydrogen discharge port, flows through the hydrogen discharge pipeline 12, enters the first water tank 7 to form saturated hydrogen rich in water, enters the humidifier 5 to humidify fresh hydrogen from the hydrogen supply tank 2, and finally, redundant hydrogen is collected from a pipeline where the hydrogen evacuation valve 50 is located.
Example 2 of the invention:
this embodiment is different from embodiment 1 in that: the humidifying component and the access mode thereof are different; the proton conducting membranes are different; the pressure in the ammonia synthesis reactor 1 is different.
The same applies except for the above differences, which will be described in detail below.
As shown in figure 2, the humidifying component is a second water tank 8, and a spraying and bubbling component for ensuring the humidifying effect is arranged in the second water tank 8, so that the hydrogen introduced into the second water tank can be fully contacted with water. One side of the second water tank 8 is communicated with a hydrogen control valve 20, and the other side is communicated with an anode gas chamber of the synthetic ammonia reactor 1.
The hydrogen from the hydrogen supply tank 2 enters the second water tank 8 after passing through a hydrogen control valve 20, and enters an anode gas chamber in the synthetic ammonia reactor 1 to participate in the reaction after being humidified.
The hydrogen discharge port in the anode gas chamber is communicated with the hydrogen discharge valve 50 to form a hydrogen discharge line in which unreacted hydrogen gas is directly discharged or collected from the hydrogen discharge port through the hydrogen discharge valve 50.
The proton conducting membrane in this example is a Nafion117 proton conducting membrane.
The working principle is as follows:
hydrogen in the hydrogen supply tank 2 enters the second water tank 8 through a hydrogen control valve 20, the humidified hydrogen enters an anode gas chamber, hydrogen protons are formed under the catalysis of power-on and platinum-based catalysts, and the hydrogen protons pass through a Nafion117 proton conducting membrane and enter the cathode side; the nitrogen in the nitrogen supply tank enters the cathode gas chamber 11 through the nitrogen control valve, and is subjected to reduction reaction under the action of power-on and gold-based catalysts and is combined with hydrogen protons passing through the Nafion115 proton conduction membrane to generate ammonia. In the process, the pressure in the cathode gas chamber is controlled to be 5MPa, and the generated pressure can directly compress the generated ammonia into liquid ammonia. The liquid ammonia enters the nitrogen separation tower 6 after passing through the first ammonia control valve 13, wherein nitrogen contained in the liquid ammonia is separated in the nitrogen separation tower 6 and is discharged or collected for reuse through a pipeline provided with a nitrogen evacuation valve 60. The liquid ammonia after nitrogen removal continuously flows in the pipeline, and then is dried under the action of calcium oxide, and finally enters the ammonia storage tank 4 through the second ammonia control valve 40.
During this process, unreacted hydrogen in the anode gas chamber will be collected from the hydrogen discharge port through the conduit provided with the hydrogen evacuation valve 50.
The present invention is not limited to the above-mentioned preferred embodiments, and any other products in various forms can be obtained by anyone in the light of the present invention, but any changes in the shape or structure thereof, which have the same or similar technical solutions as those of the present application, fall within the protection scope of the present invention.
Claims (8)
1. A system for synthesizing ammonia based on electrochemical principle is characterized in that: comprises a hydrogen supply tank, a synthetic ammonia reactor, a nitrogen supply tank and an ammonia treatment device;
the synthetic ammonia reactor comprises a membrane electrode assembly, an anode gas chamber and a cathode gas chamber;
a humidifying component is communicated with the hydrogen supply tank and is communicated with the anode gas chamber;
the nitrogen supply tank is communicated with the cathode gas chamber;
the ammonia treatment device comprises an ammonia storage tank, and the ammonia storage tank is communicated with the cathode gas chamber;
and the anode gas chamber is also provided with a hydrogen discharge port.
2. The system for synthesizing ammonia based on electrochemical principle according to claim 1, wherein: the humidifying component is a humidifier; a hydrogen gas exhaust valve for exhausting redundant hydrogen gas is communicated with the humidifier; the system also comprises a first water tank which is communicated with the hydrogen discharge port; the first water tank is communicated with the humidifier so that the unreacted hydrogen in the synthesis ammonia reactor flows back to the humidifier again.
3. The system for synthesizing ammonia based on electrochemical principle according to claim 1, wherein: the humidifying component is a second water tank, and a spraying bubbling component is arranged on the second water tank; and the hydrogen discharge port is communicated with a hydrogen discharge valve for discharging redundant hydrogen.
4. The system for synthesizing ammonia based on electrochemical principle according to claim 1, wherein: the membrane electrode assembly comprises an anode catalyst, a cathode catalyst and a proton conducting membrane; the anode catalyst and the cathode catalyst are respectively coated on two sides of the proton conducting membrane; the anode catalyst is a platinum-based catalyst; the cathode catalyst is a gold-based catalyst.
5. The system for synthesizing ammonia based on electrochemical principle according to claim 1, wherein: a hydrogen control valve is communicated between the hydrogen supply tank and the humidifying component; and a nitrogen control valve is communicated between the nitrogen supply tank and the synthesis reactor.
6. The system for synthesizing ammonia based on electrochemical principle according to claim 1, wherein: the ammonia treatment device also comprises a nitrogen separation device and a drying device; the nitrogen separation device and the drying device are arranged on a pipeline communicated with the cathode gas chamber and the ammonia storage tank in front and back.
7. The system for synthesizing ammonia based on electrochemical principles of claim 6, wherein: the nitrogen separation device is a nitrogen separation tower; the drying device is a drying channel provided with calcium oxide.
8. The system for synthesizing ammonia based on electrochemical principles of claim 7, wherein: a first ammonia control valve is arranged on a pipeline between the cathode gas chamber and the nitrogen separation tower; an emptying valve for discharging nitrogen is arranged on the nitrogen separation tower; and a second ammonia control valve is arranged on a pipeline communicated between the drying channel and the ammonia storage tank.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110928699.8A CN114959746A (en) | 2021-08-13 | 2021-08-13 | System for synthesizing ammonia based on electrochemical principle |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110928699.8A CN114959746A (en) | 2021-08-13 | 2021-08-13 | System for synthesizing ammonia based on electrochemical principle |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030164305A1 (en) * | 2002-03-04 | 2003-09-04 | Adrian Denvir | Electrochemical synthesis of ammonia |
| WO2015037445A1 (en) * | 2013-09-10 | 2015-03-19 | 旭硝子株式会社 | Ammonia production method, cell, and electrode |
| CN105264118A (en) * | 2013-03-26 | 2016-01-20 | 俄亥俄州立大学 | Electrochemical synthesis of ammonia in alkaline media |
| US20190368483A1 (en) * | 2018-05-30 | 2019-12-05 | Panasonic Intellectual Property Management Co., Ltd. | Hydrogen supply system and driving method of hydrogen supply system |
| US20190382903A1 (en) * | 2016-07-21 | 2019-12-19 | Thyssenkrupp Industrial Solutions Ag | Process for electrochemical preparation of ammonia |
| US20210155491A1 (en) * | 2019-11-21 | 2021-05-27 | OHMIUM, Inc., | Systems and methods of ammonia synthesis |
-
2021
- 2021-08-13 CN CN202110928699.8A patent/CN114959746A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030164305A1 (en) * | 2002-03-04 | 2003-09-04 | Adrian Denvir | Electrochemical synthesis of ammonia |
| CN105264118A (en) * | 2013-03-26 | 2016-01-20 | 俄亥俄州立大学 | Electrochemical synthesis of ammonia in alkaline media |
| WO2015037445A1 (en) * | 2013-09-10 | 2015-03-19 | 旭硝子株式会社 | Ammonia production method, cell, and electrode |
| US20190382903A1 (en) * | 2016-07-21 | 2019-12-19 | Thyssenkrupp Industrial Solutions Ag | Process for electrochemical preparation of ammonia |
| US20190368483A1 (en) * | 2018-05-30 | 2019-12-05 | Panasonic Intellectual Property Management Co., Ltd. | Hydrogen supply system and driving method of hydrogen supply system |
| US20210155491A1 (en) * | 2019-11-21 | 2021-05-27 | OHMIUM, Inc., | Systems and methods of ammonia synthesis |
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