CN116716620A - Water electrolysis hydrogen production system - Google Patents
Water electrolysis hydrogen production system Download PDFInfo
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- CN116716620A CN116716620A CN202310703051.XA CN202310703051A CN116716620A CN 116716620 A CN116716620 A CN 116716620A CN 202310703051 A CN202310703051 A CN 202310703051A CN 116716620 A CN116716620 A CN 116716620A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 150
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 150
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 141
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 49
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 26
- 239000004020 conductor Substances 0.000 claims abstract description 70
- 239000003792 electrolyte Substances 0.000 claims abstract description 69
- 239000001301 oxygen Substances 0.000 claims abstract description 69
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 69
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 68
- 230000033001 locomotion Effects 0.000 claims abstract description 17
- 239000013543 active substance Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 150000002431 hydrogen Chemical class 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- 239000011149 active material Substances 0.000 claims description 14
- 239000013067 intermediate product Substances 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000004891 communication Methods 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 6
- 239000003011 anion exchange membrane Substances 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical group [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 1
- 230000004323 axial length Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 1
- AIBQNUOBCRIENU-UHFFFAOYSA-N nickel;dihydrate Chemical compound O.O.[Ni] AIBQNUOBCRIENU-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- C25B9/30—Cells comprising movable electrodes, e.g. rotary electrodes; Assemblies of constructional parts thereof
-
- 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
-
- 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
-
- 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
- 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
- C25B9/63—Holders for electrodes; Positioning of the electrodes
-
- 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
Abstract
The application provides a hydrogen production system by water electrolysis. In the electrolytic water hydrogen production system, along with the cyclic movement process of the conductor flexible belt, a plurality of auxiliary electrodes are driven by the conductor flexible belt to sequentially enter the electrolyte in the hydrogen evolution container and the electrolyte in the oxygen evolution container, so that hydrogen and oxygen are generated in a way that the separated hydrogen evolution container and the separated oxygen evolution container are separated from each other and are not mixed, the hydrogen with very high purity can be obtained without post-treatment, and the collection, transportation and storage of the hydrogen are facilitated. In addition, the proton exchange membrane and the anion exchange membrane can be omitted in the water electrolysis hydrogen production system, so that a so-called membraneless water electrolysis hydrogen production system is formed, and the cost of the water electrolysis hydrogen production system is reduced. Moreover, in the electrolytic water hydrogen production system of the present application, the electrolytic water hydrogen production system can continuously operate to produce hydrogen without loss of active substances and sufficient and continuous energization of electrolyte, thereby ensuring the demand of large-scale industrial production.
Description
Technical Field
The application relates to the field of hydrogen energy preparation, in particular to a water electrolysis hydrogen production system.
Background
As global industrial and economic activities continue to expand, the need to reduce carbon emissions has become an urgent issue. To solve this problem, hydrogen is considered as a next generation energy source because it has the characteristics of zero carbon emission, no toxic by-products, high energy density (unit mass), and the like. Currently, fossil fuels are used industrially to produce hydrogen and electrolyzed water is used to produce hydrogen. The production of hydrogen from fossil fuels does not meet the requirements for sustainable development from the standpoint of environmental protection and energy consumption. The hydrogen is prepared by adopting the electrolyzed water, so that the raw material sources are wide, the price is low, the preparation process is clean, and the product purity is high. In addition, the electric energy for preparing hydrogen by using the electrolyzed water can be converted from new energy sources such as solar energy, wind energy, water energy, geothermal energy and the like, and the conversion between the sustainable energy sources can not only realize the storage of the renewable energy sources into chemical fuel by converting the electrolyzed water, but also make up the gap of sustainable supply of the energy sources in time and space, so that the preparation of hydrogen by using the electrolyzed water is a green hydrogen production route with good development prospect.
In the existing process of preparing hydrogen by using electrolyzed water (hydrogen production by using electrolyzed water), hydrogen and oxygen are simultaneously generated after the water is electrolyzed, and the hydrogen and the oxygen are mixed with each other, which not only requires post-treatment but also brings inconvenience and even danger for collection, transportation, storage and the like of the hydrogen, so that the mixing of the hydrogen and the oxygen is not expected to occur in the process of preparing hydrogen by using electrolyzed water. For this reason, in the existing electrolytic water hydrogen production system, separation of hydrogen and oxygen is mainly achieved by separating the generation areas of hydrogen and oxygen in the electrolytic cell by a proton exchange membrane or an anion exchange membrane. However, proton exchange membranes and anion exchange membranes are costly and still require post-treatment, which lengthens the production chain and further increases the cost.
Disclosure of Invention
The present application has been made in view of the above state of the art. The application aims to provide a novel water electrolysis hydrogen production system which can realize water electrolysis hydrogen production at lower cost, so that generated hydrogen and oxygen are initially separated, and the hydrogen production system is favorable for preparing high-purity hydrogen.
In order to achieve the above object, the present application may adopt the following technical solutions.
The application provides a water electrolysis hydrogen production system, which comprises the following components:
a hydrogen separation vessel in which an electrolyte containing liquid water is contained;
an oxygen evolution container which accommodates an electrolyte containing liquid water therein and is disposed in a non-communicating manner with the hydrogen evolution container;
a first electrode inserted into the electrolyte of the hydrogen evolution container;
a second electrode inserted into the electrolyte of the oxygen evolution container;
an auxiliary electrode circulation mechanism including a plurality of auxiliary electrodes and a conductor flexible belt, the plurality of auxiliary electrodes being provided to the conductor flexible belt in a spaced-apart manner from each other and being in electrically conductive communication with the conductor flexible belt, each of the auxiliary electrodes including an active material, the conductor flexible belt having a closed annular shape and being capable of circulating movement along a predetermined trajectory, the plurality of auxiliary electrodes having a first potential difference between them and a second potential difference between them,
in the process of circulating movement of the conductor flexible belt, the plurality of auxiliary electrodes are driven by the conductor flexible belt to enter the electrolyte in the hydrogen evolution container and the electrolyte in the oxygen evolution container, so that the active substances generate intermediate products and hydrogen by utilizing the first potential difference, and then the intermediate products react with the electrolyte in the oxygen evolution container to be reduced into the active substances and generate oxygen by utilizing the second potential difference.
In an alternative, the auxiliary electrode circulation mechanism is configured such that M1 auxiliary electrodes always exist for entering the electrolyte of the hydrogen evolution container and M2 auxiliary electrodes always exist for entering the electrolyte of the oxygen evolution container during the cyclic movement of the conductor flexible belt, wherein m1=m2+.gtoreq.3.
In another alternative, the first electrode is formed in a flat plate shape and has a first electrode side surface having the largest area, each of the auxiliary electrodes is formed in a flat shape and has an auxiliary electrode side surface having the largest area, and the auxiliary electrode of the electrolyte entering the hydrogen separation vessel moves in such a manner that the auxiliary electrode side surface is parallel to the first electrode side surface; and/or
The second electrode is formed in a flat plate shape and has a second electrode side surface having the largest area, and each of the auxiliary electrodes is formed in a flat shape and has an auxiliary electrode side surface having the largest area, and the auxiliary electrode of the electrolyte entering the hydrogen separation vessel moves in such a manner that the auxiliary electrode side surface is parallel to the second electrode side surface.
In another alternative, the auxiliary electrode circulation mechanism further includes:
at least one drive roll for driving the power source;
the first limit roller is positioned above the hydrogen evolution container; and
a second limiting roller which is positioned above the oxygen evolution container,
the conductor flexible belt is wound on the at least one driving roller, the first limiting roller and the second limiting roller, so that the conductor flexible belt can perform circulating motion under the driving of the at least one driving roller, the plurality of auxiliary electrodes can be limited by the first limiting roller to sink into the electrolyte of the hydrogen evolution container, and the plurality of auxiliary electrodes can be limited by the second limiting roller to sink into the electrolyte of the oxygen evolution container.
In another alternative, the auxiliary electrode circulation mechanism further includes a tension roller located at a position between the first limit roller and the second limit roller, the conductor flexible tape being wound around and tensioned by the tension roller.
In another alternative, the auxiliary electrode includes a substrate made of a porous conductor and an active material layer attached to the porous conductor.
In another alternative, each auxiliary electrode further includes a connection wire made of a conductor, one end of the connection wire is connected to the conductor flexible strip, and the other end of the connection wire is connected to the corresponding base body, so that the conductor flexible strip is electrically connected to the base body via the connection wire.
In another alternative, the distance between two adjacent auxiliary electrodes on the conductor flexible tape is greater than the length of either of the two auxiliary electrodes.
In another alternative, the absolute value of the first potential difference is greater than or equal to 1.35V and the absolute value of the second potential difference is less than 1.30V.
In another alternative, the first electrode is a platinum mesh, platinum sheet or platinum carbon electrode, and the second electrode is a carbon rod, iridium mesh or nickel mesh.
By adopting the technical scheme, the application provides a novel water electrolysis hydrogen production system. The electrolytic water hydrogen production system comprises a hydrogen evolution container, an oxygen evolution container, a first electrode, a second electrode and an auxiliary electrode circulating mechanism which are assembled together. The hydrogen evolution container and the oxygen evolution container are arranged spaced apart from each other and respectively receive an electrolyte containing liquid water, a first electrode is inserted into the electrolyte of the hydrogen evolution container, and a second electrode is inserted into the electrolyte of the oxygen evolution container. Further, a plurality of auxiliary electrodes and a conductive flexible belt are included in the auxiliary electrode circulation mechanism. A plurality of auxiliary electrodes are disposed on and in electrical communication with the conductive flexible strip in a spaced apart relationship with each other, each auxiliary electrode including an active material. The flexible conductor strip is capable of circulating along a predetermined trajectory. In addition, a first potential difference exists between the auxiliary electrode and the first electrode, and a second potential difference exists between the second electrode and the auxiliary electrode. In the process of the cyclic movement of the conductor flexible belt, the plurality of auxiliary electrodes are driven by the conductor flexible belt to enter the electrolyte in the hydrogen evolution container and the electrolyte in the oxygen evolution container, so that the active substances generate intermediate products and hydrogen by utilizing a first potential difference between the auxiliary electrodes and the first electrodes, and then the intermediate products react with the electrolyte in the oxygen evolution container to reduce the active substances and generate oxygen by utilizing a second potential difference between the auxiliary electrodes and the second electrodes.
In this way, because the hydrogen and the oxygen are respectively generated in the separated hydrogen evolution container and the oxygen evolution container, the hydrogen and the oxygen can be generated in a way of being separated from each other and not mixed, the hydrogen can be obtained without post-treatment, the purity of the hydrogen is improved, and the collection, the transportation and the storage of the hydrogen are facilitated. Further, the solution of forming an intermediate product and hydrogen gas in two spaced apart vessels with an active substance (e.g. nickel hydroxide) in one vessel and then reducing the intermediate product to nickel hydroxide in the other vessel, allows omitting the proton exchange membrane and the anion exchange membrane, thereby forming a so-called membraneless electrolyzed water hydrogen production system, reducing the cost of the electrolyzed water hydrogen production system. Moreover, it can be appreciated that in the electrolytic water hydrogen production system of the present application, the hydrogen can be continuously produced without loss of active material and sufficient electrolyte replenishment and continuous energization, thereby ensuring the need for large-scale industrial production.
Drawings
Fig. 1 is a schematic diagram showing the structure of a water electrolysis hydrogen production system according to an embodiment of the present application.
Fig. 2 is a schematic diagram showing a partial structure of the water electrolysis hydrogen production system in fig. 1.
Fig. 3-5 are graphs for illustrating the performance of the water electrolysis hydrogen production system of fig. 1.
Description of the reference numerals
1. A hydrogen evolution container;
2. an oxygen evolution container;
3. a first electrode;
4. a second electrode;
5 auxiliary electrode circulation mechanism; 51 auxiliary electrodes; a 52 conductor flexible strip; 53 drive rolls; 54 a first stop roller; 55 a second limit roller; 56 tensioning rollers.
Detailed Description
Exemplary embodiments of the present application are described below with reference to the accompanying drawings. It should be understood that these specific illustrations are for the purpose of illustrating how one skilled in the art may practice the application, and are not intended to be exhaustive of all of the possible ways of practicing the application, nor to limit the scope of the application.
A water electrolysis hydrogen production system according to an embodiment of the present application is described below with reference to the drawings.
An electrolyzed water hydrogen production system according to an embodiment of the present application is for continuously producing hydrogen and oxygen in a separated manner from electrolyzed water. As shown in fig. 1, the electrolytic water hydrogen production system includes a hydrogen evolution vessel 1, an oxygen evolution vessel 2, a first electrode 3, a second electrode 4, and an auxiliary electrode circulation mechanism 5, which are assembled together.
In the present embodiment, as shown in fig. 1 and 2, the hydrogen separation vessel 1 is formed in a cubic shape and has an opening that opens upward. An electrolyte containing potassium hydroxide (KOH) as a solute and liquid water, which may be pure water, as a solvent, is contained in the hydrogen separation vessel 1. In the hydrogen separation vessel 1, the liquid level position of the electrolyte may be set as needed, and for example, the auxiliary electrode 51 that enters the hydrogen separation vessel 1 may be set so as to be completely immersed in the electrolyte. In addition, the electrolyte may be adjusted according to the performance of the first electrode 3, and the electrolyte may be an alkaline electrolyte, a neutral electrolyte, or an acidic electrolyte.
In this embodiment, as shown in fig. 1 and 2, the oxygen evolution container 2 is formed in a cubic shape and has an opening that opens upward. The oxygen evolution vessel 2 is spaced apart from the hydrogen evolution vessel 1 and the internal spaces of both are not communicated. An electrolyte solution containing potassium hydroxide as a solute and liquid water as a solvent, which may be pure water, is contained in the oxygen evolution container 2. In the oxygen evolution vessel 2, the liquid level of the electrolyte may be set as needed, and for example, the auxiliary electrode 51 that enters the oxygen evolution vessel 2 may be set so as to be immersed in the electrolyte entirely. In addition, the electrolyte may be adjusted according to the performance of the second electrode 4, and the electrolyte may be an alkaline electrolyte, a neutral electrolyte, or an acidic electrolyte.
In the present embodiment, the first electrode 3 is a counter electrode and may be a platinum mesh, a platinum sheet or a platinum carbon electrode. As shown in fig. 1, the first electrode 3 is formed in a flat plate shape as a whole and has a first electrode side surface having the largest area, and a part of the first electrode 3 is inserted into the electrolyte of the hydrogen evolution container 1.
In this embodiment, the second electrode 4 is a counter electrode and may be a carbon rod, iridium mesh or nickel mesh. As shown in fig. 1, the second electrode 4 is formed in a flat plate shape as a whole and has a second electrode side surface having the largest area, and a part of the second electrode 4 is inserted into the electrolyte of the oxygen evolution container 2.
In the present embodiment, as shown in fig. 1, the auxiliary electrode circulation mechanism 5 includes a plurality of auxiliary electrodes 51, a conductor flexible belt 52, and a plurality of rollers 53, 54, 55, 56. The plurality of auxiliary electrodes 51 are disposed at the conductor flexible tape 52 in a spaced apart manner from each other and are in electrical communication with the conductor flexible tape 52, and the conductor flexible tape 52 is configured to have a closed loop shape and is wound around the plurality of rollers 53, 54, 55, 56 and is capable of being brought into endless motion by the plurality of rollers 53, 54, 55, 56 in a tensioned state to follow a predetermined trajectory. Therefore, this auxiliary electrode circulation mechanism 5 may also be referred to as a so-called trolley electrode circulation mechanism. It will be appreciated that in the present application, the conductor flex 52 is not limited to the strip form shown in fig. 1, but may also take the form of a chain.
Specifically, each auxiliary electrode 51 includes a base body, an active material layer, and a connection line. The matrix is made of a porous conductor, and a typical example of a material of the porous conductor is a foamed metal material such as foamed nickel. The foam nickel is a foam spongy structure body which is made of metal nickel through processing and has three-dimensional full-through mesh, the specific gravity of the foam nickel is 0.2 to 0.3, the nickel frameworks are hollow and are mutually connected in a metallurgical state, and the porosity is as high as 96-98%. The active material layer is attached to the surface of the porous conductor (where the surface includes the inner surface of the pores), the active material layer contains an active material and can be attached to the substrate by coating, and a typical example of the active material is nickel hydroxide (Ni (OH) 2 ) Cobalt hydroxide (Co (OH) 2 ) Or nickel-iron layered double hydroxide (NiFeLDH). The above-mentioned active substances do not generate gaseous by-products during the reaction in the hydrogen evolution vessel 1, and thus are advantageous in ensuring the purity of the generated hydrogen. The connection line is made of a conductor (e.g., a metal material), one end of the connection line is connected to the conductor flexible strip 52, for example, by welding, and the other end of the connection line is connected to the corresponding base body, for example, by welding, so that the conductor flexible strip 52 is electrically connected to all the base bodies of the auxiliary electrodes 51 via the connection line. In addition, the distance between two adjacent auxiliary electrodes 51 along the conductor flexible belt 52 is greater than the length of any one auxiliary electrode 51 of the two auxiliary electrodes 51, that is, greater than the total length of both the connecting line and the base body of the motor 51 in the drawing, so that the adjacent auxiliary electrodes 51 can be prevented from interfering with the conductor flexible belt 52 in the circulating motion process as much as possible.
Further, the conductor flexible belt 52 may be made of a conductor material such as stainless steel, and the conductor flexible belt 52 has sufficient flexibility to be wound around the respective rollers along the trajectory shown in fig. 1 so that the conductor flexible belt 52 can be circulated along a predetermined trajectory. In the process of producing hydrogen by electrolysis of water, as shown in fig. 2, one power source is used to provide a first potential difference between the conductive flexible strip 52 (i.e., the plurality of auxiliary electrodes 51) and the first electrode 3, and another power source is used to provide a second potential difference between the conductive flexible strip 52 (i.e., the plurality of auxiliary electrodes 51) and the second electrode 4. Specifically, the positive electrode of one power supply is electrically connected to the conductive flexible tape 52 (i.e., the plurality of auxiliary electrodes 51) and the negative electrode is electrically connected to the first electrode 3. The positive electrode of the other power source is in electrical communication with the second electrode 4 and the positive electrode is in electrical communication with the flexible strip 52 (i.e., the plurality of auxiliary electrodes 51). For 1mol/L of electrolyte comprising potassium hydroxide, the absolute value of the first potential difference may be greater than or equal to 1.35V, and is generally not greater than 1.8V, so that chemical reactions that produce oxygen in the hydrogen evolution vessel 1 can be avoided as much as possible; for 1mol/L of electrolyte comprising potassium hydroxide, the absolute value of the second potential difference is less than 1.3V, so that chemical reactions that produce hydrogen in the oxygen evolution vessel 2 can be avoided as much as possible. In the cyclic movement process, the plurality of auxiliary electrodes 51 are driven by the conductor flexible belts 52 to sequentially enter the electrolyte in the hydrogen evolution container 1 and the electrolyte in the oxygen evolution container 2, so that the potential difference between the auxiliary electrodes 51 and the first electrodes 3 is utilized to enable active substances to generate intermediate products and hydrogen, and then the potential difference between the auxiliary electrodes 51 and the second electrodes 4 is utilized to enable the intermediate products to react with liquid water in the oxygen evolution container 2 to reduce the active substances and generate oxygen. In the case of using nickel hydroxide as an active material, the intermediate product is nickel oxyhydroxide (NiOOH), and the chemical formula of reduction after hydrogen generation from nickel hydroxide as an active material is described below:
4Ni(OH) 2 →4NiOOH+2H 2 ，
4NiOOH+2H 2 O→4Ni(OH) 2 +O 2 。
based on the two formulas, the process of electrolyzing water into hydrogen and oxygen is decomposed into two independent chemical reactions, thereby avoiding mixing between hydrogen and oxygen.
With the auxiliary electrode circulation mechanism 5, on the one hand, the auxiliary electrode circulation mechanism 5 is configured such that M1 auxiliary electrodes 51 are always present in the electrolyte of the hydrogen evolution vessel 1 while M2 auxiliary electrodes 51 are present in the electrolyte of the oxygen evolution vessel 2 during the cyclic movement of the conductor flexible belt 52, wherein m1=m2+.gtoreq.3. In this way, not only the speed of continuously generating hydrogen can be ensured under the specific voltage condition, but also the speed of generating intermediate products by the active substances of the auxiliary electrode 51 is basically the same as the speed of reducing the active substances by the intermediate products, so that the active substances in the system are prevented from being excessively fast lost, and the service life of the whole system is ensured.
On the other hand, each auxiliary electrode 51 is formed in a flat shape and has an auxiliary electrode side surface having the largest area, the auxiliary electrode 51 of the electrolyte solution that enters the hydrogen separation vessel 1 moves in such a manner that the auxiliary electrode side surface is parallel to the first electrode side surface, and the auxiliary electrode 51 of the electrolyte solution that enters the hydrogen separation vessel 1 moves in such a manner that the auxiliary electrode side surface is parallel to the second electrode side surface. In this way, the side surface of the auxiliary electrode 51 with the largest area entering the hydrogen evolution container 1 and the oxygen evolution container 2 is opposite to the side surface of the first electrode 3 and the second electrode 4 with the largest area, which is beneficial to the current stabilization between the motors 3 and 4 and the auxiliary electrode 51, thereby being beneficial to the smooth process of the hydrogen production by water electrolysis.
Further, each of the plurality of rollers 53, 54, 55, 56 is rotatable about a rotation center axis of the son itself. As shown in fig. 1, the plurality of rollers 53, 54, 55, 56 includes two drive rollers 53, two first limit rollers 54, two second limit rollers 55, and one tension roller 56. The two driving rollers 53 are in transmission connection with the power source, and the two driving rollers 53 can rotate under the driving of the power source, so that the conductor flexible belt 52 wound around the driving rollers 53, the first limiting roller 54, the second limiting roller 55 and the tensioning roller 56 is driven to perform circulating movement along a preset track in a tensioning state. The two first limiting rollers 54 are located above the hydrogen separation vessel 1 in a spaced-apart manner, and the auxiliary electrode 51 provided on the portion of the conductor flexible tape 52 that is limited by the two first limiting rollers 54 can be limited to sink into the electrolyte of the hydrogen separation vessel 1. The two second limiting rollers 55 are located above the oxygen evolution container 2, and the auxiliary electrode 51 provided on the portion of the conductor flexible tape 52 limited by the two second limiting rollers 55 can be limited to sink into the electrolyte of the oxygen evolution container 2. The tension roller 56 is located at a position between the first limit roller 54 and the second limit roller 55, and the conductor flexible tape 52 is wound around the tension roller 56 and is tensioned by the tension roller 56. It will be appreciated that the first and second stop rollers 54, 55 can also act as a tension.
By adopting the technical scheme, the electrolytic water hydrogen production system according to the embodiment of the application can adopt a method for continuously decoupling electrolytic water. Specifically, in the above-described electrolytic water hydrogen production system, the electrode containing the active material is used as the dynamic auxiliary electrode 51, the auxiliary electrode 51 containing the active material is dynamically circulated into the hydrogen evolution vessel 1 and the oxygen evolution vessel 2, and the hydrogen evolution reaction and the oxygen evolution reaction independently occur in the hydrogen evolution vessel 1 and the oxygen evolution vessel 2, respectively, whereby the hydrogen evolution reaction and the oxygen evolution reaction of the electrolytic water are separated to achieve decoupling, and hydrogen gas is generated from the first electrode 3 in the hydrogen evolution vessel 1 and oxygen gas is generated from the second electrode 4 in the oxygen evolution vessel 2. Thus, the electrolytic water hydrogen production system realizes the conversion from electric energy to chemical energy, and the decoupled hydrogen-oxygen separation mode ensures that the prepared hydrogen has higher purity (the purity exceeds 99.9%). Moreover, the active substances are basically not lost in the working process, so that the process of producing hydrogen by water electrolysis can be continuously carried out. Furthermore, in the water electrolysis hydrogen production system, high-purity hydrogen can be prepared without a proton exchange membrane and an ion exchange membrane, so that the use of expensive proton exchange membranes and ion exchange membranes adopted by the existing water electrolysis hydrogen production system can be avoided, the cost is greatly reduced, and the production efficiency and the energy conversion efficiency of the whole system are improved. Moreover, since the auxiliary electrode 51 is convenient to maintain and replace, it is advantageous to realize large-scale industrial production.
It should be understood that the above-described embodiments are merely exemplary and are not intended to limit the present application. Those skilled in the art can make various modifications and changes to the above-described embodiments without departing from the scope of the present application. The following is a supplementary explanation of the technical scheme of the present application.
i. It will be appreciated that the electrolyzed water hydrogen production system according to the present application comprises a hydrogen collection module for collecting hydrogen produced from the first electrode 3.
in the above embodiment, the auxiliary electrode 51 sequentially enters the electrolyte in the hydrogen evolution vessel 1 and the electrolyte in the oxygen evolution vessel 2 during the cyclic movement of the conductor flexible tape 52 in one direction, but the present application is not limited thereto. Even if the conductor flexible belt 52 is circularly moved in the other direction, it is possible that the auxiliary electrode 51 sequentially enters the electrolyte in the oxygen evolution container 2 and the electrolyte in the hydrogen evolution container 1.
in the above embodiment, it was explained that the auxiliary electrode circulation mechanism 5 is configured such that during the cyclic movement of the conductor flexible belt 52, there are always M1 electrolytes of the auxiliary electrodes 52 into the hydrogen evolution vessel 1, and there are always M2 electrolytes of the auxiliary electrodes 52 into the oxygen evolution vessel 2, but the present application is not limited thereto. The above embodiment is preferable, and in theory, it may be set so that M1 is not less than 1 and M2 is not less than 1, or it may be set so that at some time, no auxiliary electrode 52 enters the electrolyte in the hydrogen evolution vessel 1 or no auxiliary electrode 52 enters the electrolyte in the oxygen evolution vessel 2, and even if M1 and M2 are not equal, normal operation of the system is not affected.
it will be appreciated that in the auxiliary electrode circulation mechanism 5, the number of the driving rollers 53 may be only one, and the power source drivingly connected to the driving rollers 53 to transmit torque to the driving rollers 53 may be a motor. In addition, in order to avoid interference of the auxiliary electrode 52 with the plurality of rollers during operation of the auxiliary electrode circulation mechanism 5, the width of the conductor flexible tape 1 may be set to be larger than the axial length of each roller, and the auxiliary electrode 52 may be connected to a portion of the conductor flexible tape 1 beyond each roller. In an alternative, rollers are provided at both widthwise ends of the conductor flexible tape 51 to support the conductor flexible tape 51 such that a central portion of the conductor flexible tape 51 is separated from the rollers, and the auxiliary electrode 52 is fixedly connected to the central portion of the conductor flexible tape 1.
v. it will be appreciated that the application of the electrolytic water hydrogen production system according to the application may be for waste water, sea water, and that the robustness of the system enables operation with low quality or intermittent power sources, possibly in combination with renewable energy technologies such as solar energy.
The performance of the electrolytic water hydrogen production system shown in fig. 1 according to an embodiment of the present application is shown in fig. 3-5.
Specifically, the relationship between the first potential difference and the second potential difference and the durations of both the hydrogen evolution reaction and the oxygen evolution reaction is shown in fig. 3, wherein the abscissa represents the durations of the hydrogen evolution reaction and the oxygen evolution reaction (in seconds) and the ordinate represents the absolute values of the first potential difference and the second potential difference (in V). As shown in fig. 3, the charging represents a first potential difference, and in a state where the first potential difference is greater than or equal to 1.35V, the hydrogen evolution reaction can be continuously performed without interruption; the discharge represents a second potential difference, and in a state where the second potential difference is less than 1.30V, the oxygen evolution reaction can be continuously performed without interruption.
Further, in fig. 4, a comparison result of hydrogen gas actually generated by the hydrogen evolution reaction and hydrogen gas theoretically generated and a comparison result of oxygen gas actually generated by the oxygen evolution reaction and oxygen gas theoretically generated are shown, wherein the abscissa indicates the duration (in seconds) of the hydrogen evolution reaction and the oxygen evolution reaction, the left ordinate indicates the volumes (in milliliters) of the target gases (hydrogen gas and oxygen gas) generated, and the right ordinate indicates the magnitude (dimensionless) of faraday efficiency. As shown in fig. 4, by comparing the volume of the hydrogen gas actually generated and the volume of the hydrogen gas theoretically generated at different times are substantially the same, and the volume of the oxygen gas actually generated and the volume of the oxygen gas theoretically generated at different times are also substantially the same. Thus, the faraday efficiency of the overall system is always above 95% and very close to 100%.
Further, a graph of the voltage applied to the first electrode as a function of the number of cycles of the auxiliary electrode cycle mechanism is shown in fig. 5, wherein the abscissa represents the number of cycles of the auxiliary electrode cycle mechanism (in weeks) and the ordinate is the voltage applied to the first electrode (in V). When the first electrode is supplied with the first voltage from, for example, one external power source of the electrochemical workstation, as shown in fig. 5, the voltage applied to the first electrode can be kept stable at about 1.5V as the number of cycles of the auxiliary electrode cycle mechanism increases (150 weeks or more), and thus it is found that the hydrogen production operation by the water electrolysis hydrogen production system according to the embodiment of the present application can be stably maintained for a long period of time.
Claims (10)
1. A system for producing hydrogen by electrolysis of water, comprising:
a hydrogen separation vessel (1) in which an electrolyte containing liquid water is contained;
an oxygen evolution container (2) which accommodates an electrolyte containing liquid water therein and is disposed in a non-communicating manner with the hydrogen evolution container (1);
a first electrode (3) inserted into the electrolyte of the hydrogen evolution container (1);
a second electrode (4) inserted into the electrolyte of the oxygen evolution container (2);
an auxiliary electrode circulation mechanism (5) comprising a plurality of auxiliary electrodes (51) and a conductor flexible tape (52), the plurality of auxiliary electrodes (51) being disposed in the conductor flexible tape (52) in spaced apart relation to each other and in electrical communication with the conductor flexible tape (52), each of the auxiliary electrodes (51) comprising an active substance, the conductor flexible tape (52) having a closed annular shape and being capable of circulating movement along a predetermined trajectory, the plurality of auxiliary electrodes (51) and the first electrode (3) having a first potential difference therebetween and the second electrode (4) and the plurality of auxiliary electrodes (51) having a second potential difference therebetween,
in the process of circulating movement of the conductor flexible belt (52), the plurality of auxiliary electrodes (51) are driven by the conductor flexible belt (52) to enter the electrolyte in the hydrogen evolution container (1) and the electrolyte in the oxygen evolution container (2), so that the active substances generate intermediate products and hydrogen by utilizing the first potential difference, and then the intermediate products react with the electrolyte in the oxygen evolution container (2) to be reduced into the active substances and generate oxygen by utilizing the second potential difference.
2. The electrolytic water hydrogen production system according to claim 1, wherein the auxiliary electrode circulation mechanism (5) is configured such that M1 number of the auxiliary electrodes (51) always exist in the electrolyte of the hydrogen evolution vessel (1) and M2 number of the auxiliary electrodes (51) simultaneously exist in the electrolyte of the oxygen evolution vessel (2) during the cyclic movement of the conductor flexible belt (52), wherein m1=m2+.3.
3. The water electrolysis hydrogen production system according to claim 2, wherein,
the first electrode (3) is formed in a flat plate shape and has a first electrode side surface having the largest area, each of the auxiliary electrodes (51) is formed in a flat shape and has an auxiliary electrode side surface having the largest area, and the auxiliary electrode (51) of the electrolyte entering the hydrogen separation vessel (1) moves in such a manner that the auxiliary electrode side surface is parallel to the first electrode side surface; and/or
The second electrode (4) is formed in a flat plate shape and has a second electrode side surface having the largest area, each of the auxiliary electrodes (51) is formed in a flat shape and has an auxiliary electrode side surface having the largest area, and the auxiliary electrode (51) of the electrolyte entering the hydrogen separation vessel (1) moves in such a manner that the auxiliary electrode side surface is parallel to the second electrode side surface.
4. A system for producing hydrogen from electrolyzed water according to any of claims 1 to 3, characterized in that the auxiliary electrode circulation mechanism (5) further comprises:
at least one drive roll (53) for driving the coupling with the power source;
a first limit roller (54) located above the hydrogen evolution container (1); and
a second limiting roller (55) which is positioned above the oxygen evolution container (2),
the conductor flexible belt (52) is wound on the at least one driving roller (53), the first limiting roller (54) and the second limiting roller (55), so that the conductor flexible belt (52) can perform circulating motion under the driving of the at least one driving roller (53), the plurality of auxiliary electrodes (51) can be limited by the first limiting roller (54) and sunk into the electrolyte of the hydrogen evolution container (1), and the plurality of auxiliary electrodes (51) can be limited by the second limiting roller (55) and sunk into the electrolyte of the oxygen evolution container (2).
5. The electrolytic water hydrogen production system according to claim 4, wherein the auxiliary electrode circulation mechanism (5) further includes a tension roller (56), the tension roller (56) being located at a position between the first limit roller (54) and the second limit roller (55), the conductor flexible tape (52) being wound around the tension roller (56) and being tensioned by the tension roller (56).
6. A system for producing hydrogen from electrolyzed water according to any of claims 1 to 3 characterized in that the auxiliary electrode (51) comprises a substrate made of a porous conductor and an active material layer attached to the porous conductor.
7. The electrolytic water hydrogen production system according to claim 6, wherein each of the auxiliary electrodes (51) further includes a connection wire made of a conductor, one end of the connection wire being connected to the conductor flexible strip (52), the other end of the connection wire being connected to the corresponding base body such that the conductor flexible strip (52) is electrically connected to the base body via the connection wire.
8. The water electrolysis hydrogen production system according to claim 7 wherein the distance between two adjacent auxiliary electrodes (51) on the conductor flex (52) is greater than the length of either of the two auxiliary electrodes (51).
9. A water electrolysis hydrogen production system according to any one of claim 1 to 3,
the absolute value of the first potential difference is greater than or equal to 1.35V,
the absolute value of the second potential difference is less than 1.30V.
10. A water electrolysis hydrogen production system according to any one of claim 1 to 3,
the first electrode (3) is a platinum net, a platinum sheet or a platinum carbon electrode,
the second electrode (4) is a carbon rod, an iridium net or a nickel net.
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