CN114059086A - Device and method for two-step electrolytic hydrogen production based on acidic electrolyte - Google Patents
Device and method for two-step electrolytic hydrogen production based on acidic electrolyte Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 139
- 239000001257 hydrogen Substances 0.000 title claims abstract description 138
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 239000003792 electrolyte Substances 0.000 title claims abstract description 37
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims abstract description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 39
- 230000008021 deposition Effects 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000006260 foam Substances 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 239000003014 ion exchange membrane Substances 0.000 abstract description 4
- 150000002431 hydrogen Chemical class 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007832 Na2SO4 Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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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
-
- 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
- C25B1/21—Manganese oxides
-
- 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
- C25B1/50—Processes
-
- 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
- C25B15/087—Recycling of electrolyte to electrochemical cell
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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
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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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- Sustainable Development (AREA)
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Abstract
The invention belongs to the technical field of water electrolysis, and particularly relates to a device and a method for producing hydrogen by two-step electrolysis based on an acidic electrolyte. The device comprises an electrolytic tank, and a hydrogen evolution electrode, a deposition electrode and a Mn-containing material disposed in the tank2+The acid electrolyte of (1). The hydrogen production process comprises two steps: electrolytic production of hydrogen comprising H+Electrochemical reduction at the cathode to produce hydrogen gas with Mn in the electrolyte2+Is electrochemically oxidized at the anode to formMnO2Precipitation and H+(ii) a Reduction of MnO2Including adding a reducing agent to the can to form MnO2Reduction of the precipitate to Mn2+The electrolyte is dissolved in the electrolyte and is continuously used for electrolytic hydrogen production, or the electrolyte is discharged out of the tank, and hydrogen production is continuously carried out after the electrolyte is updated; the two steps can be cyclically alternated. Compared with the traditional hydrogen production by acid electrolysis of water, the method does not involve the simultaneous production of hydrogen and oxygen, does not need an ion exchange membrane to separate two electrodes, directly generates high-pressure hydrogen, and greatly reduces the electrolysis cost.
Description
Technical Field
The invention belongs to the technical field of water electrolysis, and particularly relates to a device and a method for producing hydrogen by two-step water electrolysis based on an acidic electrolyte.
Background
With the continuous development of society and the continuous improvement of technology, people have higher and higher requirements on energy. Coal, oil and natural gas are currently the major energy sources. However, the fossil energy sources are limited in reserves and non-renewable, and the large-scale use of the fossil energy sources brings about the problems of greenhouse gas emission, environmental pollution and the like while greatly improving the productivity of human society and the living standard of people. In order to relieve the contradiction between the energy shortage and the economic development and the environmental protection, the development of low-carbon renewable clean energy becomes a common target of the international society, and is beneficial to the sustainable development of the world.
Among low-carbon clean renewable energy sources including solar energy and wind energy, hydrogen energy is receiving attention due to its advantage of high efficiency and stability. The electrolysis of water is the most important way to produce hydrogen, and a great deal of research is being conducted on the hydrogen by using water resources widely distributed on the earth as the source of hydrogen. Alkaline water electrolysis is the most mature and industrialized water electrolysis technology, but the process simultaneously generates hydrogen and oxygen, the product needs to be further separated, and the purity is difficult to guarantee; the method is characterized in that generated hydrogen and oxygen are simply separated, transmembrane leakage of gas still occurs, overpotential of hydrogen evolution and oxygen evolution and ion transmembrane transportation needs to be overcome during electrolysis, so that electrolysis voltage is large, the requirement on current is high, direct preparation of higher-pressure hydrogen is limited due to poor mechanical strength of the proton exchange membrane, and cost pressure which is not negligible is brought by high price.
Mn2+/MnO2Is widely used as a positive electrode material for aqueous zinc batteries and proton batteries. Although its potential in acidic solution is close to the oxidation potential of water, it is due to its good electrochemical reversibility，Mn2+The oxidation of (a) can often be carried out at a small overpotential. In acidic solution, Mn2+Can be electrochemically oxidized to MnO before oxygen evolution reaction occurs2And (4) precipitating. And Mn2+By oxidation to form MnO2Deposited on the anode and separated from the liquid phase, avoiding its re-reduction on the cathode. Therefore, we will refer to Mn2+Anodic reaction of oxidative deposition and H+The cathode reduction reaction is combined, and a novel device and a novel method for producing hydrogen by electrolysis are developed. The concrete description is as follows.
Disclosure of Invention
The invention aims to overcome the difficulty of water electrolysis and provides a device and a method for producing hydrogen by two-step water electrolysis based on an acid electrolyte, which have high hydrogen production efficiency, high purity and low cost.
The invention utilizes Mn2+/MnO2As redox mediator, so that oxidation of water does not occur during electrolysis, and MnO2After being formed, the hydrogen is deposited on the deposition electrode and is separated from the hydrogen evolution electrode, so that high-purity hydrogen is obtained at lower voltage and higher efficiency. The invention is different from the traditional proton exchange membrane acid electrolyzed water, does not need an ion exchange membrane to separate the two electrodes, can directly generate high-pressure hydrogen and greatly reduce the electrolysis cost.
The invention provides a device for producing hydrogen by two-step water electrolysis based on an acid electrolyte, which comprises a sealable electrolytic tank, and a hydrogen evolution electrode (cathode), a deposition electrode (anode) and Mn-containing electrolyte which are arranged in the electrolytic tank2+The acid electrolyte of (1).
In the invention, the hydrogen evolution electrode has catalytic activity for the electrochemical hydrogen evolution process. Specifically, the hydrogen evolution electrode is: one or more composite electrodes of a platinum-plated titanium mesh, a platinum-plated titanium foam, a platinum-plated copper mesh, a platinum-plated copper foam, a platinum-plated stainless steel mesh, carbon paper loaded with a platinum-carbon catalyst, a carbon felt loaded with a platinum-carbon catalyst, carbon cloth loaded with a platinum-carbon catalyst, a graphite felt loaded with a platinum-carbon catalyst, a titanium mesh loaded with a platinum-carbon catalyst, a titanium sheet loaded with a platinum-carbon catalyst, titanium foam loaded with a platinum-carbon catalyst, a copper mesh loaded with a platinum-carbon catalyst, copper foam loaded with a platinum-carbon catalyst, and a graphite electrode loaded with a platinum-carbon catalyst.
In the invention, the deposition electrode is a manganese dioxide deposition dissolution reaction site. The deposition electrode is: one or more composite electrodes of carbon felt, carbon cloth, carbon paper, graphite felt, titanium mesh, titanium foam and stainless steel mesh.
In the present invention, a porous separator may also be placed between the hydrogen evolution electrode and the precipitation electrode to prevent short circuits.
In the present invention, the electrolyte contains H+And Mn2+An acidic aqueous solution of (a); wherein, the acid (H)+) Has a concentration of 0.0001 to 10 mol/L and contains Mn2+The concentration of (b) is 0.001-5 mol/L.
In the invention, the acid in the acidic aqueous solution is one or a mixture of sulfuric acid, nitric acid, phosphoric acid, perchloric acid and methane sulfonic acid.
In the invention, the electrolyte can also contain one or a mixture of more of sulfate, nitrate, phosphate, perchlorate and methane sulfonate, and is mainly used for improving the ionic conductivity of the electrolyte.
In the invention, the electrolytic tank can be square or cylindrical and comprises a closable gas outlet, a closable liquid outlet and a closable liquid inlet. The gas outlet is mainly used for discharging the generated hydrogen; the liquid outlet is mainly used for discharging the electrolyte; the liquid inlet can be added with electrolyte and/or solution containing reducing agent.
In the present invention, the solution containing the reducing agent is mainly used for MnO to be deposited2 Reduction to soluble Mn2+。
In the invention, the reducing agent can be one or a mixture of more of sulfur dioxide, hydrazine hydrate, sodium hydrosulfite, sodium sulfite, oxalic acid, sodium oxalate, ferrous salt, hydroxylamine hydrochloride, sodium thiosulfate and sodium hypophosphite.
The invention further provides a hydrogen production method based on the device and based on the two-step water electrolysis of the fully acidic electrolyte, which comprises the following specific steps:
hydrogen production by electrolysis:
in the electrolytic tank, H+Is electrochemically reduced to H at the hydrogen evolution cathode2Collected via the hydrogen outlet, i.e. 2H++ 2e-→ H2↑；Mn2+Electrochemically oxidized to MnO at the anode deposition electrode2And deposit of Mn2++ 2H2O- 2e-→MnO2 + 4H+；
(II) manganese dioxide reduction:
adding reducing agent into electrolytic tank, stirring thoroughly, MnO2Is reduced to Mn2+Dissolved from the anode-deposited electrode, MnO2+ 2e- + 4H+→ Mn2++ 2H2O；
The reduced electrolyte can be directly used for electrolytic hydrogen production, or discharged through a liquid outlet and then supplemented with new electrolyte through a liquid inlet.
The step (I) and the step (II) are alternately carried out to realize the preparation of high-purity hydrogen.
Compared with the prior art, the invention has the beneficial effects that:
the most remarkable characteristic of the electrolytic tank designed by the invention is that Mn in acidic electrolyte is utilized2+/MnO2As redox mediators, the electrolyzed water is decomposed into two steps, so that the oxidation of water does not occur in the process of electrolytic hydrogen production, and Mn2+Oxidation to form solid MnO2The hydrogen is deposited on the anode deposition electrode and separated from the hydrogen evolution electrode, and the coulomb efficiency of the cathode hydrogen reduction is improved, so that high-purity hydrogen is obtained at lower voltage and higher efficiency. Meanwhile, the invention does not need an ion exchange membrane and uses a sealable electrolytic tank, and can directly obtain high-purity high-pressure hydrogen.
Compared with the traditional hydrogen production by acid electrolysis of water, the method does not involve the simultaneous production of hydrogen and oxygen, does not need an ion exchange membrane to separate two electrodes, directly generates high-pressure hydrogen, and greatly reduces the electrolysis cost. In addition, unstable renewable energy sources, such as wind energy, solar energy and the like, can be directly used for the electrolysis reaction of the device, and the conversion of the renewable energy sources into hydrogen energy is promoted.
Drawings
FIG. 1 is a device and a method for producing hydrogen by two-step electrolysis based on an acid electrolyte.
FIG. 2 shows a 1.6V constant-voltage hydrogen production curve by electrolysis.
FIG. 3 shows a 100mA constant current hydrogen production curve by electrolysis in an electrolytic tank.
Detailed Description
To further clearly illustrate the technical solutions and advantages of the present invention, the present invention is described by the following specific examples, but the present invention is not limited to these examples.
Example 1
The electrolytic tank was placed in a 40 ml bath containing 0.5 mol/L Na2SO41 mol/l MnSO40.5 mol/l H2SO4The hydrogen evolution catalytic cathode electrode adopts a platinum-plated titanium mesh with the thickness of 10 square centimeters, and the anode deposition electrode adopts a graphite felt with the thickness of 10 square centimeters which is subjected to heat treatment at the temperature of 400 ℃ in the air. Constant voltage electrolysis is carried out by adopting direct current with 1.6 volts, the initial current is 179 milliamperes, the current is stabilized at 177 milliamperes after 30 minutes, the average current is 187 milliamperes, and the electric quantity flowing through the electrolytic tank is 93.4 milliamperes. The hydrogen produced was collected via the hydrogen outlet and the volume of hydrogen was 42.1 ml as measured by 25 ℃ bleed. The coulomb efficiency of hydrogen production calculated according to Faraday's law was 94.4%. An aqueous solution containing 0.5g of sodium sulfite was then added to the electrolytic tank and stirred for a period of time to fully reduce the manganese dioxide. The steps are repeated for 50 times, the initial current of the 50 th time is 190 milliamperes, the current is stabilized at 165 milliamperes after 30 minutes, the average current is 177 milliamperes, and the electric quantity flowing through the electrolytic tank is 88.4 milliamperes. The hydrogen produced was collected via the hydrogen outlet and the volume of hydrogen was 40.1 ml as measured by 25 ℃ bleed. The coulomb efficiency of hydrogen production was calculated to be 95.0% according to faraday's law. The purity of the gas generated twice is verified, and the purity of the generated hydrogen is extremely high. (FIG. 2) (see Table 1).
Example 2
The electrolytic tank is placed with 40 ml of MnSO with the concentration of 1 mol/l40.5 mol/l H2SO4The hydrogen evolution catalytic cathode electrode adopts 10 square centimeters of carbon cloth loaded with platinum-carbon catalyst, and the anode deposition electrode adopts 10 which is thermally treated at 400 ℃ in the airSquare centimeter carbon cloth. Constant voltage electrolysis is carried out by adopting direct current of 1.6 volts, the initial current is 296 milliamperes, the current is stabilized at 188 milliamperes after 30 minutes, the average current is 211 milliamperes, and the electric quantity flowing through an electrolysis tank is 105.6 milliamperes. The hydrogen produced was collected via the hydrogen outlet and the hydrogen volume was 48.4 ml as measured by 25 ℃ bleed. The coulomb efficiency of hydrogen production calculated according to Faraday's law was 96.0%. 200 microliters of 50% hydrazine hydrate was then added to the electrolytic tank and stirred for a period of time to fully reduce the manganese dioxide. The steps are repeated for 50 times, the initial current of the 50 th time is 201 milliamperes, the current is stabilized at 185 milliamperes after 30 minutes, the average current is 191 milliamperes, and the electric quantity flowing through the electrolytic tank is 95.6 milliamperes. The hydrogen produced was collected via the hydrogen outlet and the hydrogen volume was 44.1 ml as measured by 25 ℃ bleed. The coulomb efficiency of hydrogen production was calculated to be 96.7% according to faraday's law. The purity of the gas generated twice is verified, and the purity of the generated hydrogen is extremely high. (see Table 1).
Example 3
The electrolytic tank is placed with 40 ml of MnSO with the concentration of 1 mol/l 41 mol/l H2SO4The hydrogen evolution catalytic cathode electrode adopts a platinum-plated titanium mesh with the thickness of 10 square centimeters, and the anode deposition electrode adopts a graphite felt with the thickness of 10 square centimeters which is subjected to heat treatment at the temperature of 400 ℃ in the air. Constant current electrolysis was carried out using 100 milliamps direct current at an initial voltage of 1.53 volts, after 30 minutes the voltage stabilized at 1.49 volts, the average voltage was 1.48 volts, and the amount of electricity flowing through the electrolysis cell was 49.8 milliamps. The hydrogen produced was collected via the hydrogen outlet and the hydrogen volume was 22.5 ml as measured by 25 ℃ bleed. The coulomb efficiency of hydrogen production calculated according to Faraday's law was 94.6%. An aqueous solution containing 0.5g of sodium dithionite is then added to the electrolytic cell and stirred for a period of time sufficient to reduce the manganese dioxide. The above steps are repeated for 50 times, the 50 th time has the initial voltage of 1.50 volts, the voltage is stabilized at 1.51 volts after 30 minutes, the average voltage is 1.50 volts, and the electric quantity flowing through the electrolytic tank is 49.9 milliampere hours. The hydrogen produced was collected via the hydrogen outlet and the volume of hydrogen was 22.0 ml as measured by 25 ℃ bleed. The coulomb efficiency of hydrogen production was calculated to be 92.4% according to faraday's law. For two generationThe purity of the generated hydrogen is proved to be extremely high. (FIG. 3) (see Table 1).
Example 4
The electrolytic tank was placed in a 40 ml bath containing 0.5 mol/L Na2SO40.5 mol/l MnSO 41 mol/l H2SO4The hydrogen evolution catalytic cathode electrode adopts 10 square centimeters of graphite felt loaded with platinum-carbon catalyst, and the anode deposition electrode adopts 10 square centimeters of graphite felt which is thermally treated at 400 ℃ in the air. Constant current electrolysis was carried out using 200 milliamps direct current at an initial voltage of 1.53 volts, after 30 minutes the voltage stabilized at 1.55 volts, the average voltage was 1.54 volts, and the amount of electricity flowing through the electrolysis cell was 100.0 milliamps. The hydrogen produced was collected via the hydrogen outlet and the volume of hydrogen was 46.0 ml as measured by 25 ℃ bleed. The coulomb efficiency of hydrogen production calculated according to Faraday's law was 96.6%. An aqueous solution containing 0.5g of sodium sulfite was then added to the electrolytic tank and stirred for a period of time to fully reduce the manganese dioxide. The above steps are repeated for 50 times, the 50 th time has the initial voltage of 1.53 volts, the voltage is stabilized at 1.56 volts after 30 minutes, the average voltage is 1.54 volts, and the electric quantity flowing through the electrolytic tank is 99.9 milliampere hours. The hydrogen produced was collected via the hydrogen outlet and the volume of hydrogen was 45.0 ml as measured by 25 ℃ bleed. The coulomb efficiency of hydrogen production calculated according to Faraday's law was 94.5%. The purity of the gas generated twice is verified, and the purity of the generated hydrogen is extremely high. (see Table 1).
Example 5
The electrolytic tank was placed in a 40 ml tank containing 0.5 mol/L K2SO41 mol/l MnSO40.5 mol/l H2SO4The hydrogen evolution catalysis cathode electrode adopts 10 square centimeters of carbon cloth loaded with platinum-carbon catalysts, and the anode deposition electrode adopts 10 square centimeters of carbon cloth which is subjected to heat treatment at 400 ℃ in the air. Constant current electrolysis was carried out using 500 milliamps direct current with an initial voltage of 1.96 volts, a voltage stabilized at 1.88 volts after 30 minutes, an average voltage of 1.85 volts, and an amount of electricity flowing through the electrolysis cell of 249.8 milliamps. The generated hydrogen is collected through a hydrogen outlet and measured by a 25 ℃ water discharge method to obtain hydrogenThe gas volume was 105.1 ml. The coulomb efficiency of hydrogen production calculated according to Faraday's law was 96.6%. An aqueous solution containing 1g of ferrous sulfate heptahydrate is then added to the electrolytic tank, stirred for a period of time to fully reduce the manganese dioxide, and the electrolytic tank is then emptied and the same electrolyte is added initially. The above steps are repeated for 50 times, the 50 th time has the initial voltage of 1.89V, the voltage is stabilized at 1.84V after 30 minutes, the average voltage is 1.85V, and the electric quantity flowing through the electrolytic tank is 249.9 mAmp. The hydrogen produced was collected via the hydrogen outlet and the hydrogen volume was 107.9 ml as measured by 25 ℃ bleed. The coulomb efficiency of hydrogen production calculated according to Faraday's law was 94.5%. The purity of the gas generated twice is verified, and the purity of the generated hydrogen is extremely high. (see Table 1).
Example 6
The electrolytic tank is placed with 40 ml of MnSO with the concentration of 1 mol/l40.5 mol/l H2SO4The hydrogen evolution catalytic cathode electrode adopts foamed nickel of platinum-carbon catalyst loaded by 10 square centimeters, and the anode deposition electrode adopts foamed nickel. Constant voltage electrolysis is carried out by adopting direct current of 1.8 volts, the initial current is 420 milliamperes, the current is stabilized at 411 milliamperes after 30 minutes, the average current is 409 milliamperes, and the electric quantity flowing through the electrolytic tank is 204.4 milliamperes. The hydrogen produced was collected via the hydrogen outlet and the volume of hydrogen was 86.1 ml as measured by 25 ℃ bleed. The coulomb efficiency of hydrogen production was calculated to be 96.7% according to faraday's law. An aqueous solution containing 2g of sodium thiosulfate was then added to the electrolytic tank, stirred for a period of time to fully reduce the manganese dioxide, and the electrolytic tank was then emptied and the same initial electrolyte was added. The steps are repeated for 50 times, the 50 th initial current is 434 milliamperes, the current is stabilized at 430 milliamperes after 30 minutes, the average current is 433 milliamperes, and the electric quantity flowing through the electrolytic tank is 216.5 milliamperes. The hydrogen produced was collected via the hydrogen outlet and the hydrogen volume was 91.9 ml as measured by 25 ℃ bleed. The hydrogen production coulomb efficiency calculated according to Faraday's law is 97.5%. The purity of the gas generated twice is verified, and the purity of the generated hydrogen is extremely high. (see Table 1).
Example 7
The electrolytic tank is placed with 40 mlContaining 0.5 mol/l Na2SO41 mol/l MnSO40.5 mol/l H2SO4The hydrogen evolution catalytic cathode electrode adopts a 10 square centimeter platinized stainless steel mesh, and the anode deposition electrode adopts a 10 square centimeter carbon felt which is heat treated at 400 ℃ in the air. Constant voltage electrolysis is carried out by adopting direct current of 1.6 volts, the initial current is 159 milliamperes, the current is stabilized at 166 milliamperes after 30 minutes, the average current is 167 milliamperes, and the electric quantity flowing through the electrolytic tank is 83.4 milliamperes. The hydrogen produced was collected via the hydrogen outlet and the hydrogen volume was 38.1 ml as measured by 25 ℃ bleed. The coulomb efficiency of hydrogen production was calculated to be 95.7% according to faraday's law. An aqueous solution containing 0.4g of sodium oxalate was then added to the electrolytic tank and stirred for a period of time sufficient to reduce the manganese dioxide. The steps are repeated for 50 times, the initial current of the 50 th time is 175 milliamperes, the current is stabilized at 167 milliamperes after 30 minutes, the average current is 174 milliamperes, and the electric quantity flowing through the electrolytic tank is 86.9 milliamperes. The hydrogen produced was collected via the hydrogen outlet and the volume of hydrogen was 37.6 ml as measured by 25 ℃ bleed. The coulomb efficiency of hydrogen production calculated according to Faraday's law was 90.7%. The purity of the gas generated twice is verified, and the purity of the generated hydrogen is extremely high. (FIG. 2).
(see Table 1).
TABLE 1 Hydrogen production results for a two-step electrolytic hydrogen production plant based on acid electrolytes with different compositions
Claims (8)
1. The device for producing hydrogen by two-step water electrolysis based on acid electrolyte is characterized by comprising a sealable electrolytic tank, a hydrogen evolution electrode serving as a cathode, a deposition electrode serving as an anode and a hydrogen-containing anode2+The acid electrolyte of (1);
the hydrogen evolution electrode has catalytic activity to the electrochemical hydrogen evolution process;
the deposition electrode is used for manganese dioxide deposition dissolution reaction;
a porous diaphragm is arranged between the hydrogen evolution electrode and the deposition electrode and is used for preventing short circuit;
the electrolyte contains H+And Mn2+An acidic aqueous solution of (a);
the electrolytic tank is provided with a closable gas outlet, a closable liquid outlet and a closable liquid inlet; the gas outlet is mainly used for discharging the generated hydrogen; the liquid outlet is mainly used for discharging the electrolyte; the liquid inlet is used for adding electrolyte and/or solution containing a reducing agent.
2. The device according to claim 1, wherein the hydrogen evolution electrode is selected from one or more composite electrodes of a platinized titanium mesh, platinized titanium foam, a platinized copper mesh, platinized copper foam, a platinized stainless steel mesh, carbon paper loaded with a platinum carbon catalyst, a carbon felt loaded with a platinum carbon catalyst, carbon cloth loaded with a platinum carbon catalyst, a graphite felt loaded with a platinum carbon catalyst, a titanium mesh loaded with a platinum carbon catalyst, a titanium sheet loaded with a platinum carbon catalyst, titanium foam loaded with a platinum carbon catalyst, a copper mesh loaded with a platinum carbon catalyst, copper foam loaded with a platinum carbon catalyst, and a graphite electrode loaded with a platinum carbon catalyst.
3. The device according to claim 1, wherein the deposition electrode is one or more composite electrodes selected from carbon felt, carbon cloth, carbon paper, graphite felt, titanium mesh, titanium foam and stainless steel mesh.
4. The apparatus of claim 1, wherein the electrolyte contains an acid (H)+) Has a concentration of 0.0001 to 10 mol/L and contains Mn2+The concentration of (b) is 0.001-5 mol/L.
5. The device according to claim 1, wherein the acid in the acidic aqueous solution is selected from one or more of sulfuric acid, nitric acid, phosphoric acid, perchloric acid and methane sulfonic acid.
6. The device according to claim 1, wherein the electrolyte further comprises one or more of sulfate, nitrate, phosphate, perchlorate and methane sulfonate.
7. The apparatus according to claim 1, wherein the reducing agent is selected from one or more of sulfur dioxide, hydrazine hydrate, sodium dithionite, sodium sulfite, oxalic acid, sodium oxalate, ferrous salt, hydroxylamine hydrochloride, sodium thiosulfate and sodium hypophosphite.
8. A method for producing hydrogen by two-step water electrolysis based on acid electrolyte based on the device of any one of claims 1 to 8, which is characterized by comprising the following specific steps:
hydrogen production by electrolysis:
in the electrolytic tank, H+Is electrochemically reduced to H at the hydrogen evolution cathode2Collected via the hydrogen outlet, i.e. 2H++ 2e-→ H2↑； Mn2+Electrochemically oxidized to MnO at the anode deposition electrode2And deposit of Mn2++ 2H2O- 2e-→MnO2 + 4H+；
(II) manganese dioxide reduction:
adding reducing agent into electrolytic tank, stirring thoroughly, MnO2Is reduced to Mn2+Dissolved from the anode-deposited electrode, MnO2+ 2e- + 4H+→ Mn2++ 2H2O；
The reduced electrolyte is directly used for electrolytic hydrogen production, or is discharged through a liquid outlet and then is supplemented with new electrolyte through a liquid inlet;
the step (I) and the step (II) are alternately carried out to realize the preparation of high-purity hydrogen.
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| CN102634656A (en) * | 2012-04-19 | 2012-08-15 | 四川大学 | Method for preparing electrolytic manganese/electrolytic manganese dioxide by cyclically leaching manganese oxide with sulfur and calcium |
| CN113737204A (en) * | 2021-09-27 | 2021-12-03 | 昆明理工大学 | Preparation of MnO by anode electrolysis in strong acid medium2Auxiliary high-efficiency hydrogen production method |
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| CN102634656A (en) * | 2012-04-19 | 2012-08-15 | 四川大学 | Method for preparing electrolytic manganese/electrolytic manganese dioxide by cyclically leaching manganese oxide with sulfur and calcium |
| CN113737204A (en) * | 2021-09-27 | 2021-12-03 | 昆明理工大学 | Preparation of MnO by anode electrolysis in strong acid medium2Auxiliary high-efficiency hydrogen production method |
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| CN114457352A (en) * | 2022-02-23 | 2022-05-10 | 复旦大学 | Device and method for producing hydrogen by stepwise electrolysis of water based on acidic electrolyte |
| CN114457352B (en) * | 2022-02-23 | 2023-11-24 | 复旦大学 | Device and method for hydrogen production by stepwise electrolysis of water based on acidic electrolyte |
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