CN110820008A - Water electrolytic cell for absorbing hydrogen by organic liquid - Google Patents
Water electrolytic cell for absorbing hydrogen by organic liquid Download PDFInfo
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- CN110820008A CN110820008A CN201911182899.2A CN201911182899A CN110820008A CN 110820008 A CN110820008 A CN 110820008A CN 201911182899 A CN201911182899 A CN 201911182899A CN 110820008 A CN110820008 A CN 110820008A
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- cathode
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- liquid
- organic liquid
- membrane electrode
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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
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
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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
Abstract
The invention provides a water electrolytic cell for absorbing hydrogen by using organic liquid, which comprises: membrane electrode, anode cavity, cathode cavity, anode solution, organic liquid hydrogen storage material; wherein, the upper part of the two side cavities of the membrane electrode is gas, the lower part of the two side cavities is liquid, the two sides of the membrane electrode are immersed in the liquid and contacted with the liquid, the liquid in the cathode side cavity is organic liquid hydrogen storage material, and the anode and the cathode of the membrane electrode are respectively connected with the cathode and the anode of the direct current power supply. The invention can effectively reduce the manufacturing cost of the device, simplify the equipment, provide the heat required by water electrolysis by utilizing the heat released by the hydrogenation reaction of the organic liquid and improve the energy utilization rate and the operating efficiency of the system.
Description
Technical Field
The application relates to the field of environmental protection, in particular to a water electrolytic cell for absorbing hydrogen by using organic liquid.
Background
At present, the hydrogenation reaction of the organic liquid hydrogen storage material needs to be completed in a special hydrogenation reactor. When the organic liquid is used for storing hydrogen prepared by water electrolysis, two sets of equipment, namely a water electrolyzer and a hydrogenation reactor, are needed, so that the equipment is large in size and low in efficiency.
Therefore, the water electrolysis bath is combined with the organic liquid hydrogenation device, the manufacturing cost of the device can be effectively reduced, the equipment is simplified, heat required by water electrolysis is provided by utilizing the heat released in the organic liquid hydrogenation reaction, and the energy utilization rate and the operation efficiency of the system are improved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a water electrolytic cell for absorbing hydrogen by using organic liquid, which uses a set of integrated equipment to complete hydrogen production reaction by water electrolysis and absorb hydrogen simultaneously. The invention discloses a water electrolytic cell for absorbing hydrogen by using organic liquid, which aims to solve the problems of large volume and low operation efficiency of the prior art.
The invention discloses a water electrolytic cell for absorbing hydrogen by using organic liquid, which comprises: membrane electrode, anode cavity, cathode cavity, anode solution, organic liquid hydrogen storage material; wherein:
the upper part of the two side cavities of the membrane electrode is gas, the lower part of the two side cavities of the membrane electrode is liquid, the two sides of the membrane electrode are immersed in the liquid and are contacted with the liquid, the liquid in the cathode side cavity is an organic liquid hydrogen storage material, and the anode and the cathode of the membrane electrode are respectively connected with the cathode and the anode of a direct current power supply.
The membrane electrode is composed of a high-temperature proton exchange membrane, electrode catalysts and a porous current collector, wherein the electrode catalysts are loaded on two sides of the membrane electrode, and the membrane electrode is phosphoric acid doped with PBI.
The liquid in the anode cavity is phosphoric acid aqueous solution.
The melting point of the organic liquid hydrogen storage material in the cathode side cavity is not higher than 70 ℃, and the adopted materials include but are not limited to ethyl carbazole, propyl carbazole, methyl indole, ethyl indole, dibenzyl toluene, benzyl toluene and the mixture thereof.
The device comprises a water pump connected with the anode cavity, an organic liquid delivery pump connected with the cathode cavity, and an organic liquid outlet valve arranged below the liquid level of the cathode side cavity.
And the gas sides of the anode and the cathode are respectively provided with an anode pressure sensor, an anode deflation valve, a cathode pressure sensor and a cathode deflation valve.
Inert gases are filled in the anode cavity and the cathode cavity.
The hydrogen absorption chemical reaction of the water electrolysis cell for absorbing hydrogen by using organic liquid is carried out on the cathode side of the membrane electrode. Compared with the prior art, the invention has the advantages that the water electrolyzer is combined with the organic liquid hydrogenation device, the device cost can be effectively reduced, the equipment is simplified, the heat required by water electrolysis is provided by utilizing the heat released by the organic liquid hydrogenation reaction, and the energy utilization rate and the operating efficiency of the system are improved.
Drawings
In order to more clearly explain the technical solution of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious to those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a structural view of a water electrolytic cell that absorbs hydrogen gas using an organic liquid.
The reference numbers in the above figures are as follows:
1-a membrane electrode; 2-anode cavity; 3-cathode chamber; 4-aqueous phosphoric acid solution; 5-an organic liquid hydrogen storage material; 6-water pump; 7-organic liquid delivery pump; 8-organic liquid outlet valve; 9-anode pressure sensor; 10-anode air release valve; 11-cathode pressure sensor; 12-cathode purge valve.
Detailed Description
Referring to fig. 1, there is shown a structural view of a water electrolytic cell for absorbing hydrogen gas using an organic liquid.
The water electrolytic cell for absorbing hydrogen by using organic liquid provided by the application can specifically comprise the following structures: the device comprises a membrane electrode 1, an anode cavity 2, a cathode cavity 3, a phosphoric acid aqueous solution 4, an organic liquid hydrogen storage material 5, a water pump 6, an organic liquid delivery pump 7, an organic liquid outlet valve 8, an anode pressure sensor 9, an anode deflation valve 10, a cathode pressure sensor 11 and a cathode deflation valve 12.
In practical application, the electrolytic cell is heated to 110-160 ℃; the anode cavity and the cathode cavity are filled with inert gas, the pressure difference between the two cavities is kept below 50kPa, and meanwhile, the pressure of the anode side cavity 2 is higher than the saturated vapor pressure at the current temperature so as to prevent the water in the solution from boiling.
The argon is low in cost, so that the anode cavity and the cathode cavity adopt argon.
Under the action of current, water in the phosphoric acid aqueous solution 4 is electrolyzed, and the anode of the membrane electrode 1 generates oxygen which rises above the liquid level and is converged into the gas at the upper part of the anode cavity 2; the cathode cavity 3 generates hydrogen, the hydrogen and the organic liquid hydrogen storage material 5 generate hydrogenation reaction under the action of the membrane electrode 1 catalyst to generate hydrogenated organic liquid, and part of unreacted hydrogen rises to cause the upper part of the liquid to converge into gas above the cathode cavity 3.
The water pump 6 replenishes water to the anode cavity 2 according to the consumption of the electrolyzed water, and maintains the concentration of the phosphoric acid aqueous solution 4 constant. The organic liquid transfer pump 7 injects unhydrogenated organic liquid into the cathode cavity 3 at a certain speed, and simultaneously the hydrogenated organic liquid flows out from the outlet valve 8 at a certain speed, so that the quantity of the organic liquid in the cathode cavity 3 is kept stable.
Phosphoric acid doped PBI is selected as a high-temperature proton exchange membrane, an anode catalyst can be selected as Ir, and a cathode catalyst can be selected as Pt. The electrons are conducted by means of protons on a proton exchange membrane, which is acidified with phosphoric acid in order to increase the conduction efficiency. In order to further continuously acidify the proton exchange membrane, the liquid in the anode cavity adopts phosphoric acid aqueous solution 4, and the concentration is 1-2 mol/L.
The pressure control system controls the pressure regulating valves 10 and 12 to discharge gas, the pressure difference between two sides of the regulating cavity is smaller than 50kPa, and the highest working pressure of the cavities 2 and 3 is controlled not to be larger than 3 MPa.
The melting point of the organic liquid hydrogen storage material in the cathode side cavity is not higher than 70 ℃, and the adopted materials include but are not limited to ethyl carbazole, propyl carbazole, methyl indole, ethyl indole, dibenzyl toluene, benzyl toluene and the mixture thereof. The hydrogenation reaction temperature of the N-ethyl carbazole is relatively low, about 110-120 ℃, the melting point is right, the reaction rate is high, 1 ethyl carbazole molecule can load 12H atoms, and complete hydrogenation can be realized within 1-2 hours, so that the N-ethyl carbazole is adopted as the organic liquid hydrogen storage material 5 in the cathode cavity 3.
Before the device is started, the gas sides of the anode cavity 2 and the cathode cavity 3 are replaced by Ar gas, the whole electrolytic cell and the liquid on the two sides are heated to 130 ℃, and the pressure on the two sides of the cavity rises to keep the phosphoric acid aqueous solution from boiling.
The voltage of the direct current applied to the monolithic membrane electrode does not exceed 1.7V. Oxygen generated at the anode part of the membrane electrode 1 is gathered at the anode gas side, hydrogen generated at the cathode is reacted with ethyl carbazole under the action of a catalyst to generate hydrogenated ethyl carbazole, and unreacted hydrogen at the cathode part is gathered at the cathode gas side.
Along with the electrolytic reaction, the redundant oxygen of the anode and the redundant hydrogen of the cathode are discharged through respective air release valves 10 and 12, so that the pressure of the anode cavity 2 and the pressure of the cathode cavity 3 are maintained at about 2MPa, and the pressure difference between the two electrode cavities is not more than 50 kPa. The water pump 6 continuously supplies water to the anode to supplement the consumption of the electrolytic reaction. Along with the increase of the degree of the ethyl carbazole hydrogenation reaction in the cathode cavity 3, the organic liquid outlet valve 8 is intermittently opened, the organic liquid 5 with higher hydrogenation degree in the cathode cavity 3 is removed, and meanwhile, the organic liquid delivery pump 7 is opened to supplement the non-hydrogenated organic liquid to maintain the total amount of the organic liquid in the cathode cavity 3 constant.
Through the process, the electric energy input to the electrolytic cell is converted into hydrogen, and the hydrogen is stored in the ethyl carbazole through the hydrogenation reaction generated in situ on the electrode, so that the hydrogenated ethyl carbazole is obtained.
The water electrolytic cell for absorbing hydrogen by using organic liquid provided by the invention is described in detail above, and the principle and the embodiment of the invention are explained by applying specific examples, and the description of the examples is only used for helping to understand the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (7)
1. A water electrolytic cell for absorbing hydrogen gas with an organic liquid, comprising: the membrane electrode, the anode cavity, the cathode cavity, the anode solution and the organic liquid hydrogen storage material; wherein:
the upper part of the two side cavities of the membrane electrode is gas, the lower part of the two side cavities of the membrane electrode is liquid, the two sides of the membrane electrode are immersed in the liquid and are contacted with the liquid, the liquid in the cathode side cavity is an organic liquid hydrogen storage material, and the anode and the cathode of the membrane electrode are respectively connected with the cathode and the anode of a direct current power supply.
2. The water electrolytic cell for absorbing hydrogen by using organic liquid as claimed in claim 1, wherein the membrane electrode is composed of a high temperature proton exchange membrane, both sides of which are loaded with electrode catalyst and porous current collector, and the membrane component is phosphoric acid doped with PBI.
3. The electrolytic cell of claim 1, wherein the liquid in the anode chamber is phosphoric acid aqueous solution.
4. The electrolytic cell of claim 1, wherein the organic liquid hydrogen storage material in the cathode side chamber has a melting point of no higher than 70 ℃.
5. A water electrolyser for absorbing hydrogen with organic liquids as in claim 1 further comprising a water pump connected to the anode chamber and an organic liquid delivery pump connected to the cathode chamber, and an organic liquid outlet valve mounted below the liquid level in the cathode side chamber.
6. A water electrolyser for absorbing hydrogen with organic liquids as claimed in claim 1 wherein the gas sides of said anode and said cathode are fitted with an anode pressure sensor, an anode bleed valve and a cathode pressure sensor, respectively, a cathode bleed valve.
7. The electrolytic cell of claim 1 wherein the anode chamber and the cathode chamber are filled with an inert gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201911182899.2A CN110820008A (en) | 2019-11-27 | 2019-11-27 | Water electrolytic cell for absorbing hydrogen by organic liquid |
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| CN201911182899.2A CN110820008A (en) | 2019-11-27 | 2019-11-27 | Water electrolytic cell for absorbing hydrogen by organic liquid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117004970A (en) * | 2023-10-08 | 2023-11-07 | 陕西氢易能源科技有限公司 | PEM reactor based on organic liquid electrochemical hydrogenation and system thereof |
| CN117026260A (en) * | 2023-10-08 | 2023-11-10 | 陕西氢易能源科技有限公司 | PEM reactor for electrochemical hydrogenation and system thereof |
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| CN117004970A (en) * | 2023-10-08 | 2023-11-07 | 陕西氢易能源科技有限公司 | PEM reactor based on organic liquid electrochemical hydrogenation and system thereof |
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