CN115305482B - Hydrogen production method and device by electrolysis of seawater - Google Patents
Hydrogen production method and device by electrolysis of seawater Download PDFInfo
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- CN115305482B CN115305482B CN202211043129.1A CN202211043129A CN115305482B CN 115305482 B CN115305482 B CN 115305482B CN 202211043129 A CN202211043129 A CN 202211043129A CN 115305482 B CN115305482 B CN 115305482B
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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
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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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
- C25B15/00—Operating or servicing cells
- C25B15/02—Process control or regulation
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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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
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The application provides a method and a device for producing hydrogen by electrolyzing seawater, wherein the method for producing hydrogen by electrolyzing seawater comprises the following steps: a) Corroding and activating the electrode matrix by adopting seawater, and forming a catalytic layer on the surface of the electrode matrix; b) Using seawater as electrolyte, and carrying out electrolytic hydrogen production in an electrolytic tank; in the electrolytic hydrogen production process, comparing the real-time voltage of the electrolytic tank with the original voltage, and if the real-time voltage is increased by more than 5% compared with the original voltage, performing pulse acidification washing. The application uses chloride ions in seawater to perform electrode corrosion activation, generates a catalytic layer of a layered double hydroxide structure in situ, has high active surface area and chloride ion tolerance, and simultaneously uses the pulse impulse force and the corrosion action of high-concentration acid liquor to wash the electrode surface, so that the generated scale is removed when firm combination is not formed, physical blocking loss of active sites is avoided, and high reaction activity is maintained.
Description
Technical Field
The application belongs to the field of hydrogen energy and seawater resource utilization, and particularly relates to a method and a device for producing hydrogen by electrolyzing seawater.
Background
The hydrogen production by water electrolysis is a technical method capable of realizing large-scale green hydrogen production at present, and has a vital effect on promoting the social construction of hydrogen energy and realizing a double-carbon target. The current mainstream water electrolysis hydrogen production technology comprises alkaline water electrolysis (AE) hydrogen production, proton Exchange Membrane (PEM) hydrogen production and high-temperature Solid Oxide Electrolysis (SOEC) hydrogen production, which have high requirements on the water quality of raw water, and even in areas with rich water resources, raw water can be often applied by a purification method, the water electrolysis hydrogen production process is complicated, the cost is high, and the development of the water electrolysis hydrogen production technology is limited.
The sea water has rich reserves on the earth, and the resources such as offshore wind energy, solar energy, wave energy and the like are rich. In the prior art, attempts have been made to generate electricity by using renewable energy sources on the sea coupled with the electrolysis of seawater to produce hydrogen. The seawater has high salt content, and most of the seawater in the existing offshore hydrogen production projects needs to be pretreated through reverse osmosis and other processes, so that the seawater has high treatment difficulty, high cost and unstable effluent quality, and the service life and performance of the electrolytic hydrogen production equipment are influenced.
When seawater is adopted to directly produce hydrogen, high-content chloride ions in the seawater cause serious corrosion to the metal electrode catalytic material for the current electrolytic hydrogen production, so that the performance and the service life of the material and the system are reduced. Meanwhile, calcium and magnesium ions in the seawater are combined with generated hydroxide ions to form a precipitate in the electrolysis process, so that active sites are blocked, and the catalyst is disabled.
Disclosure of Invention
In view of the above, the application aims to provide a method and a device for producing hydrogen by electrolyzing seawater, which are beneficial to avoiding forming a scaling layer on an active site and keeping high hydrogen production activity by electrolysis.
In order to achieve the above purpose, the technical scheme of the application is a method for producing hydrogen by electrolyzing seawater, comprising the following steps:
a) Corroding and activating the electrode matrix by adopting seawater, and forming a catalytic layer on the surface of the electrode matrix;
b) Using seawater as electrolyte, and carrying out electrolytic hydrogen production in an electrolytic tank; in the electrolytic hydrogen production process, comparing the real-time voltage of the electrolytic tank with the original voltage, and if the real-time voltage is increased by more than 5% compared with the original voltage, performing pulse acidification washing.
The application firstly adopts seawater to carry out corrosion activation on the electrode matrix, the corrosion activation time is more than 12 hours, and metal corrosion and in-situ deposition reaction are carried out on the surface of the electrode matrix to form a catalytic layer. The thickness of the electrode matrix is preferably 100-500 mu m, and the electrode matrix is porous or compact conductive metal selected from one or more of iron, nickel, cobalt and molybdenum. The catalytic layer is a layered double metal hydroxide, and the layered double metal hydroxide is a layered columnar compound formed by a positively charged metal hydroxide layer and interlayer filling exchangeable anions. In the process of electrode matrix corrosion activation, a micro battery is formed on the surface of the electrode matrix to generate metal corrosion, and meanwhile, the existence of chloride ions in seawater accelerates the metal corrosion process, and Ca in seawater 2+ 、Mg 2 + Plasma divalent ion and radicalThe bulk metals are co-deposited to form a layered double hydroxide structure.
After a catalytic layer is formed on the surface of the electrode matrix, seawater is used as electrolyte, and electrolytic hydrogen production is carried out in an electrolytic tank, wherein the electrolytic tank comprises an electrolytic hydrogen production unit, the electrolytic hydrogen production unit comprises a cathode, an anode and a diaphragm, and hydrogen and oxygen are respectively collected at the cathode and the anode.
In the electrolytic hydrogen production process, comparing the real-time voltage of the electrolytic tank with the original voltage, and if the real-time voltage is increased by more than 5% compared with the original voltage, performing pulse acidification washing by adopting pulse acid liquor, wherein the acid liquor is hydrochloric acid, the pulse acidification washing is to alternately wash the cathode and the anode of the electrolytic tank, and the washing time of the cathode and the anode is 1-2 min independently. The electrode surface is washed by the impulse force of impulse acid liquor and the corrosion of high concentration acid liquor, and the generated scale is removed when the firm combination is not formed. In one embodiment, in the electrolytic hydrogen production process, comparing the real-time voltage of the electrolytic tank with the original voltage, and if the real-time voltage is 5% -10% higher than the original voltage, performing pulse acidification washing.
In one embodiment, in the electrolytic hydrogen production process, comparing the real-time voltage of the electrolytic tank with the original voltage, if the electrolytic hydrogen production time is T1, the real-time voltage is increased by 5% -10% compared with the original voltage, and pulse acidification washing is carried out on the cathode of the electrolytic tank, wherein the washing time is 1-2 min; in the electrolytic hydrogen production process, comparing the real-time voltage of the electrolytic tank with the original voltage, and if the electrolytic hydrogen production time T2 is after the pulse acidification washing of the cathode of the electrolytic tank is finished, increasing the real-time voltage by 5% -10% compared with the original voltage, and performing pulse acidification washing on the anode of the electrolytic tank for 1-2 min.
The electrolytic hydrogen production method also comprises the steps of comparing the real-time PH of the seawater with the initial PH in the electrolytic hydrogen production process, and discharging the seawater as waste liquid if the real-time PH value is reduced by more than 10% compared with the initial PH value. In one embodiment, in the electrolytic hydrogen production process, the real-time PH of the seawater is compared with the initial PH, if the real-time PH value is reduced by 10-20% compared with the initial PH value, the seawater is discharged as waste liquid, and the discharge time is preferably 5-10 min.
According to the electrolytic hydrogen production method provided by the application, the layered double metal hydroxide is generated on the surface of the electrode matrix in situ through metal corrosion and in-situ deposition on the surface of the electrode matrix, the layered double metal hydroxide has larger specific surface area and porosity, and the metals have synergistic effect, so that the activity performance of the catalytic layer is improved, and the catalytic layer has higher chloride ion tolerance. In the electrolytic hydrogen production process, the electrode is subjected to pulse acidification washing, the surface of the electrode is washed by utilizing the pulse impulse of pulse acid liquor and the corrosion action of high-concentration acid liquor, and the generated scale is removed when firm combination is not formed, so that the activity of electrolytic hydrogen production can be improved.
The application also provides an electrolytic hydrogen production device which is characterized by comprising an electrolytic tank device and a seawater circulating device connected with a seawater inlet and a seawater outlet of the electrolytic tank device; an acid liquor treatment device connected with the acid liquor inlet of the electrolytic tank and a waste liquor collecting device connected with the waste liquor outlet of the electrolytic tank.
The electrolytic cell device comprises an electrolytic hydrogen production unit, wherein the electrolytic hydrogen production unit comprises a cathode, an anode and a diaphragm, a cathode chamber and an anode chamber are formed, and the cathode and the anode are mutually independent porous or compact conductive metals, preferably one or more of iron, nickel, cobalt and molybdenum; the cathode and the anode independently comprise an electrode matrix, or the cathode and the anode independently comprise an electrode matrix and layered double hydroxide compounded on the surface of the electrode matrix.
The seawater circulating device comprises a seawater storage tank, wherein an outlet of the seawater storage tank is connected with a seawater inlet of an electrolytic tank, the seawater storage tank inlet is connected with a seawater outlet of the electrolytic tank, and a seawater pump is arranged between the seawater storage tank outlet and the seawater inlet of the electrolytic tank.
The acid liquid treatment device comprises an acid liquid storage tank, wherein acid liquid in the acid liquid storage tank is hydrochloric acid, an outlet of the acid liquid storage tank is connected with an acid liquid inlet of an electrolytic tank, an acid liquid pump 1 and an acid liquid pump 2 are arranged in parallel between the outlet of the acid liquid storage tank and the acid liquid inlet of the electrolytic tank, the acid liquid pump 1 is connected with a cathode of the electrolytic tank, and the acid liquid pump 2 is connected with an anode of the electrolytic tank.
The waste liquid collecting device comprises a waste liquid storage tank, wherein the inlet of the waste liquid storage tank is connected with the waste liquid outlet of the electrolytic tank, and a waste liquid pump is arranged between the inlet of the waste liquid storage tank and the waste liquid outlet of the electrolytic tank.
In one embodiment, an electrolytic hydrogen production system includes an electrolytic tank, an acid storage tank, a seawater storage tank, a waste liquid storage tank, an acid pump, a seawater pump, and a waste liquid pump. The electrolytic tank comprises a repeated electrolytic hydrogen production unit, wherein the electrolytic hydrogen production unit comprises a cathode, a diaphragm and an anode, and a cathode chamber and an anode chamber are formed. The cathode chamber and the anode chamber are respectively provided with a seawater inlet, a seawater outlet, an acid liquid inlet and a waste liquid outlet. The seawater inlet and the waste liquid outlet of the cathode chamber and the anode chamber are respectively summarized to the same seawater inlet pipe and the same sewage discharge pipe, and the seawater outlet and the acid liquid inlet of the cathode chamber and the anode chamber are respectively summarized to different seawater outlet pipes and acid liquid inlet pipes of the cathode and the anode. The acid liquor outlet of the acid liquor storage tank is respectively connected with the inlets of the acid liquor pump 1 and the acid liquor pump 2, the outlet of the acid liquor pump 1 is connected with the acid liquor inlet of the cathode chamber of the electrolytic cell, and the outlet of the acid liquor pump 2 is connected with the acid liquor inlet of the anode chamber of the electrolytic cell. The sea water outlet of the sea water storage tank is connected with the inlet of a sea water pump, and the outlet of the sea water pump is connected with the sea water inlets of the cathode chamber and the anode chamber of the electrolytic cell. Seawater in a seawater outlet pipe of the cathode chamber of the electrolytic tank returns to a seawater storage tank after gas-liquid separation. Seawater in the seawater outlet pipe of the anode chamber of the electrolytic tank returns to the seawater storage tank after gas-liquid separation. The waste liquid outlet of the electrolytic tank is connected with the inlet of the waste liquid pump, and the outlet of the waste liquid pump is connected with the waste liquid inlet of the waste liquid storage tank.
The electrolytic hydrogen production device can be directly applied to electrolytic hydrogen production, and the application is not limited herein. In one embodiment, the electrode corrosion activation is firstly carried out, a seawater pump is turned on, an acid pump and a waste liquid pump are turned off, so that seawater circulates in an electrolytic tank system for more than 12 hours, and metal corrosion and in-situ deposition of the electrode in the electrolytic tank occur to form a catalytic layer. Then, carrying out electrolytic hydrogen production, opening a sea water pump, closing an acid liquid pump and a waste liquid pump, switching on a cathode and an anode power supply, taking sea water as electrolyte, and starting to electrolyze water in an electrolytic tank to produce hydrogen, wherein the electrolytic tank comprises an electrolytic hydrogen production unit, and the electrolytic hydrogen production unit comprises a cathode, an anode and a diaphragm, and respectively collecting hydrogen and oxygen at the cathode and the anode. In the electrolytic hydrogen production process, comparing the real-time voltage of the electrolytic tank with the original voltage, if the electrolytic hydrogen production time T1 is longer, the real-time voltage is 5% -10% higher than the original voltage, starting an acid pump 1, performing pulse acidification washing on the cathode of the electrolytic tank for 1-2 min, and closing the acid pump 1; in the electrolytic hydrogen production process, comparing the real-time voltage of the electrolytic tank with the original voltage, if the time of electrolytic hydrogen production T2 is 5% -10% higher than the original voltage after the pulse acidification washing of the cathode of the electrolytic tank is finished, starting an acid pump 2, carrying out pulse acidification washing on the anode of the electrolytic tank for 1-2 min, and closing the acid pump 2. Starting from the starting point of the electrolytic hydrogen production process, when the pH accumulated reduction of the seawater storage tank is observed to reach 10% -20% of the initial value, starting a waste liquid pump, discharging the seawater as waste liquid, preferably for 5-10 min, and closing the waste liquid pump.
The method for preparing hydrogen by electrolyzing seawater provided by the application comprises the following steps: a) Corroding and activating the electrode matrix by adopting seawater, and forming a catalytic layer on the surface of the electrode matrix; b) Using seawater as electrolyte, and carrying out electrolytic hydrogen production in an electrolytic tank; in the electrolytic hydrogen production process, comparing the real-time voltage of the electrolytic tank with the original voltage, and if the real-time voltage is increased by more than 5% compared with the original voltage, performing pulse acidification washing. In the process of electrolytic hydrogen production, the method of corrosion activation, electrolytic hydrogen production and pulse acidification washing circulation is adopted, chloride ions in seawater are utilized for corrosion activation, nano layered double metal hydroxide is generated on the surface of an electrode matrix in situ, the layered double metal hydroxide has larger specific surface area and porosity, and the metals have synergistic effect, so that the activity performance of a catalytic layer is improved, and the catalyst has higher chloride ion tolerance. Meanwhile, when the scale produced on the surface of the electrode is not firmly combined, calcium and magnesium particles formed on the surface of the electrode are washed by utilizing the impulse force and the corrosion action of high-concentration acid liquor, so that the physical blocking loss of active sites is avoided, and the high reactivity is maintained.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present application, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a hydrogen production system by electrolysis of seawater;
FIG. 2 is a schematic diagram of an electrode of an electrolytic cell in a seawater electrolysis hydrogen production system.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1:
referring to fig. 1, fig. 1 is a schematic diagram of an electrolytic seawater hydrogen production system, which comprises an electrolytic tank, an acid liquid storage tank, a seawater storage tank, a waste liquid storage tank, an acid liquid pump, a seawater pump and a waste liquid pump. The acid liquor in the acid liquor storage tank is hydrochloric acid.
The electrolytic tank comprises a repeated electrolytic hydrogen production unit, wherein the electrolytic hydrogen production unit comprises a cathode, a diaphragm and an anode, and a cathode chamber and an anode chamber are formed. The cathode chamber and the anode chamber are respectively provided with a seawater inlet, a seawater outlet, an acid liquor inlet and a waste liquid outlet. The seawater inlet and the waste liquid outlet of the cathode chamber and the anode chamber are respectively summarized to the same seawater inlet pipe and the same sewage discharge pipe, and the seawater outlet, the acid liquid inlet and the acid liquid outlet of the cathode chamber and the anode chamber are respectively summarized to different cathode and anode seawater outlet pipes and different acid liquid inlet pipes.
The sea water outlet of the sea water storage tank is connected with the inlet of a sea water pump, and the outlet of the sea water pump is connected with the sea water inlets of the cathode chamber and the anode chamber of the electrolytic cell. Seawater in a seawater outlet pipe of the cathode chamber of the electrolytic tank returns to a seawater storage tank after gas-liquid separation. Seawater in the seawater outlet pipe of the anode chamber of the electrolytic tank returns to the seawater storage tank after gas-liquid separation.
The acid liquor outlet of the acid liquor storage tank is respectively connected with the inlets of the acid liquor pump 1 and the acid liquor pump 2, the outlet of the acid liquor pump 1 is connected with the acid liquor inlet of the cathode chamber of the electrolytic cell, and the outlet of the acid liquor pump 2 is connected with the acid liquor inlet of the anode chamber of the electrolytic cell.
The waste liquid outlet of the electrolytic tank is connected with the inlet of the waste liquid pump, and the outlet of the waste liquid pump is connected with the waste liquid inlet of the waste liquid storage tank.
Example 2:
the electrolytic hydrogen production is carried out by adopting the electrolytic seawater hydrogen production system of the embodiment 1, which concretely comprises the following steps:
(1) Electrode corrosion activation: and (3) turning on a seawater pump, turning off an acid pump and a waste liquid pump to circulate the seawater in the electrolytic tank system for 12 hours, wherein an electrode matrix in the electrolytic tank is foamed nickel, and the thickness of a formed catalytic layer is 200nm. The electrode structure is shown in fig. 2, fig. 2 is a schematic diagram of an electrolytic tank electrode in the seawater electrolysis hydrogen production system, and the electrode comprises an electrode matrix and layered double hydroxide compounded on the surface of the electrode matrix. The surface of the electrode matrix undergoes metal corrosion and in-situ deposition reaction. In the corrosion process, the existence of chloride ions in the seawater accelerates the corrosion process; during the deposition process, ca in sea water 2+ 、Mg 2+ Co-depositing the divalent ions and the matrix metal to form a layered double hydroxide structure; the layered double hydroxide has larger specific surface area and porosity, and the double metals have synergistic effect, thus improving the activity of electrolytic hydrogen production.
(2) Electrolytic hydrogen production: and (3) turning on a seawater pump, turning off an acid liquid pump and a waste liquid pump, switching on a cathode power supply and an anode power supply, starting the process of producing hydrogen by electrolyzing water, and collecting hydrogen and oxygen at the cathode and the anode respectively.
(3) Pulse acidification washing: when the seawater pump is started, and when the electrolytic hydrogen production is carried out for a certain time of 12 hours, the accumulated voltage rise of the electrolytic hydrogen production is observed to reach 5% of the initial value, the acid liquid pump 1 is started, the acid liquid pump 1 is closed after the duration time is 2min, and the voltage is reduced to the initial value; after the acid liquid pump 1 is turned off, when the electrolytic hydrogen production is carried out for a certain time of 5 hours, and when the voltage accumulation of the electrolytic hydrogen production is observed to be raised to 5% of the initial value, the acid liquid pump 2 is turned on, the acid liquid pump 2 is turned off after the duration of 2 minutes, and the voltage is reduced to the initial value. Starting from the beginning of the electrolytic hydrogen production process, when the pH accumulation reduction of the seawater storage tank is observed to reach 10% of the initial value, the waste liquid pump is turned on, the seawater is discharged as waste liquid, the discharge time is preferably 10min, and the waste liquid pump is turned off.
The above description of the embodiments is only for aiding in the understanding of the method of the present application and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the application can be made without departing from the principles of the application and these modifications and adaptations are intended to be within the scope of the application as defined in the following claims.
Claims (7)
1. A method for producing hydrogen by electrolyzing seawater, comprising:
a) Carrying out corrosion activation on the electrode matrix by adopting seawater, and forming a layered double hydroxide catalytic layer on the surface of the electrode matrix;
b) Using seawater as electrolyte, and carrying out electrolytic hydrogen production in an electrolytic tank; in the electrolytic hydrogen production process, comparing the real-time voltage of the electrolytic tank with the original voltage, and if the real-time voltage is increased by more than 5% compared with the original voltage, performing pulse acidification washing;
the pulse acidification washing is to alternately wash the cathode and the anode of the electrolytic tank;
the electrode matrix is selected from one or more of iron, nickel, cobalt and molybdenum.
2. The method for producing hydrogen by electrolyzing seawater according to claim 1, wherein the washing time of the cathode and the anode are 1 to 2min independently of each other.
3. The method for producing hydrogen from seawater by electrolysis of claim 1, further comprising: in the electrolytic hydrogen production process, comparing the real-time PH value of the seawater with the initial PH value, and discharging the seawater as waste liquid if the real-time PH value is reduced by more than 10% compared with the initial PH value.
4. The method for producing hydrogen by electrolyzing seawater as claimed in claim 1, wherein the thickness of the electrode substrate is 100 to 500 μm.
5. The electrolytic hydrogen production device is characterized by comprising an electrolytic tank device and a seawater circulation device connected with a seawater inlet and a seawater outlet of the electrolytic tank device; an acid liquor treatment device connected with the acid liquor inlet of the electrolytic tank and a waste liquor collection device connected with the waste liquor outlet of the electrolytic tank;
the electrolytic cell device comprises an electrolytic hydrogen production unit, wherein the electrolytic hydrogen production unit comprises a cathode, an anode and a diaphragm;
the cathode and the anode independently comprise an electrode matrix and a layered double hydroxide catalytic layer compounded on the surface of the electrode matrix;
the electrode matrix is selected from one or more of iron, nickel, cobalt and molybdenum;
the device also comprises a pulse acidification washing device, wherein the pulse acidification washing device is used for alternately washing the cathode and the anode of the electrolytic cell.
6. The electrolytic hydrogen production apparatus according to claim 5, wherein the seawater circulation apparatus comprises a seawater storage tank, an outlet of the seawater storage tank is connected with a seawater inlet of the electrolytic tank, the seawater storage tank inlet is connected with a seawater outlet of the electrolytic tank, and a seawater pump is provided between the seawater storage tank outlet and the seawater inlet of the electrolytic tank;
the acid liquid treatment device comprises an acid liquid storage tank, wherein an outlet of the acid liquid storage tank is connected with an acid liquid inlet of the electrolytic tank, an acid liquid pump 1 and an acid liquid pump 2 are arranged in parallel between the outlet of the acid liquid storage tank and the acid liquid inlet of the electrolytic tank, the acid liquid pump 1 is connected with a cathode of the electrolytic tank, and the acid liquid pump 2 is connected with an anode of the electrolytic tank.
7. The electrolytic hydrogen production apparatus according to claim 5, wherein the waste liquid collecting device comprises a waste liquid storage tank, the inlet of the waste liquid storage tank is connected with the waste liquid outlet of the electrolytic tank, and a waste liquid pump is provided between the inlet of the waste liquid storage tank and the waste liquid outlet of the electrolytic tank.
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