CN115142079B - Dual-functional electrolysis method and system for producing ammonia and hydrogen - Google Patents
Dual-functional electrolysis method and system for producing ammonia and hydrogen Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000001257 hydrogen Substances 0.000 title claims abstract description 83
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 83
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 63
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 51
- 239000003792 electrolyte Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 238000003860 storage Methods 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 229910052723 transition metal Inorganic materials 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 150000003624 transition metals Chemical class 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- 239000008151 electrolyte solution Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- -1 transition metal sulfide Chemical class 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 3
- 229910002056 binary alloy Inorganic materials 0.000 claims description 3
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 3
- 229910002058 ternary alloy Inorganic materials 0.000 claims description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000012670 alkaline solution Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 239000003929 acidic solution Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000003411 electrode reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910001325 element alloy Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002091 nanocage Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
-
- 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
- C25B1/27—Ammonia
-
- 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
- C25B9/67—Heating or cooling means
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a dual-functional electrolysis method and system for producing hydrogen by ammonia production. The electrolysis method can realize the effect of one tank with two purposes by changing the operation condition of the electrolysis tank, and can prepare hydrogen energy and ammonia energy. The method provided by the invention heats the electrolyte when ammonia is collected, so that the temperature of water electrolysis hydrogen production is reached, the electrolyte does not need to be gradually electrolyzed again when hydrogen production is carried out by electrolysis, and the energy consumption is reduced.
Description
Technical Field
The invention relates to the technical field of hydrogen production by electrolysis of ammonia, in particular to a dual-functional electrolysis method and system for producing hydrogen by ammonia.
Background
Ammonia plays a very important role in national economy. The Haber-bosch process for industrial synthesis of ammonia requires high temperature and high pressure reaction conditions, resulting in a large amount of energy consumption and carbon emissions. Currently, the electrocatalytic nitrogen reduction (NRR) ammonia synthesis technology with zero carbon emission has great development prospect, and the electrocatalytic nitrogen reduction (NRR) technology provides a new approach for green ammonia synthesis. Besides ammonia energy, hydrogen energy as a clean energy source has the same advantages of no pollution and sustainable development. At present, along with the continuous increase of the installed capacity of renewable energy sources, the technology of hydrogen production by electrochemical technology is very mature, and the conventional technology of hydrogen production by alkaline electrolysis of water realizes the preparation of hydrogen by an electrolytic tank device. At present, the preparation of hydrogen and ammonia by an electrolysis method is realized in different electrolytic tanks, and the dual-function purpose of producing ammonia and hydrogen cannot be achieved, so that a dual-function electrolysis system for producing ammonia and hydrogen is necessary to be provided to realize the dual-purpose effect of one tank.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent.
Therefore, the invention aims to provide a dual-function electrolysis method and system for producing ammonia and hydrogen.
On one hand, the invention provides a dual-functional electrolysis method for preparing ammonia and hydrogen, which comprises the following steps:
(1) Regulating the pH value of the electrolyte to 5.5-6.5, introducing nitrogen into an ammonia separating cathode, and electrolyzing to prepare ammonia;
(2) Regulating the pH value of the electrolyte to be 13-14, heating to 70-90 ℃, and collecting ammonia gas;
(3) Changing the power-on mode, preparing hydrogen by electrolysis, and collecting hydrogen at a hydrogen evolution cathode;
(4) And (5) repeating the steps (1) - (3) to prepare ammonia and hydrogen respectively.
In some embodiments, the electrolyte is a 0.3-0.6M ammonium sulfate solution or a 0.05-0.15M sodium sulfate solution.
In some embodiments, the adjusting the pH of the electrolyte to a pH of 5.5-6.5 is accomplished by adding 80% -98% sulfuric acid solution to the electrolyte.
In some embodiments, adjusting the pH of the electrolyte to 13-14 is accomplished by adding 20% -40% by mass potassium hydroxide solution or 20% -30% by mass sodium hydroxide solution to the electrolyte solution.
In some embodiments, the ammonia-evolving cathode is one of a layered double hydroxide, a cobalt-based catalyst, a metal nitrogen doped porous carbon composite catalyst, a metal phosphide, a metal oxide, a molten iron catalyst, a molybdenum-based composite material, or a tungsten-based composite material.
In some embodiments, the hydrogen evolution cathode is one of a nickel-molybdenum alloy, molybdenum sulfide, metal phosphide, metal oxide, metal sulfide, or multi-alloy electrode.
In some embodiments, the purity of the nitrogen is above 98%.
In some embodiments, oxygen is collected at an oxygen evolving anode during electrolysis.
In some embodiments, the oxygen evolving anode is one of a NiFe-LDH, a transition metal hydroxide catalyst, a transition metal oxide catalyst, a transition metal sulfide catalyst, a transition metal phosphide catalyst, or a binary/ternary alloy catalyst of a transition metal.
In another aspect, the present invention provides a dual-function electrolysis system for producing ammonia and hydrogen, comprising:
an ammonia gas generated by electrolysis at the ammonia precipitation cathode is collected into an ammonia storage tank;
a hydrogen evolution cathode, wherein hydrogen generated by electrolysis at the hydrogen evolution cathode is collected into a hydrogen storage tank;
an oxygen-separating anode, wherein oxygen generated by electrolysis at the oxygen-separating anode is collected into an oxygen storage tank, ammonia is prepared when the ammonia-separating cathode and the oxygen-separating anode are electrified, and hydrogen is prepared when the hydrogen-separating cathode and the oxygen-separating anode are electrified;
a heater for heating the electrolyte;
and a pH meter for measuring the pH value of the electrolyte.
Compared with the prior art, the invention has the beneficial effects that:
the electrolysis method can realize the effect of one tank with two purposes by changing the operation condition of the electrolysis tank, and can prepare hydrogen energy and ammonia energy.
The method provided by the invention heats the electrolyte when ammonia is collected, so that the temperature of water electrolysis hydrogen production is reached, the electrolyte does not need to be gradually electrolyzed again when hydrogen production is carried out by electrolysis, and the energy consumption is reduced.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic diagram of a dual-function electrolysis system for producing ammonia and hydrogen;
reference numerals illustrate:
an ammonia-separating cathode 1, a hydrogen-separating cathode 2, an oxygen-separating anode 3, a pH meter 4, an ammonia storage tank 5, a hydrogen storage tank 6, an oxygen storage tank 7, a heater 8, an alkaline solution storage tank 9 and an acid solution storage tank 10.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The following describes a dual-functional electrolysis method and system for producing ammonia and hydrogen according to the embodiment of the invention with reference to the accompanying drawings.
The invention relates to a dual-functional electrolysis method for producing ammonia and hydrogen, which comprises the following steps:
(1) Regulating the pH value of the electrolyte to 5.5-6.5, introducing nitrogen into an ammonia separating cathode, and electrolyzing to prepare ammonia;
(2) Regulating the pH value of the electrolyte to be 13-14, heating to 70-90 ℃, and collecting ammonia gas;
(3) Changing the power-on mode, preparing hydrogen by electrolysis, and collecting hydrogen at a hydrogen evolution cathode;
(4) And (5) repeating the steps (1) - (3) to prepare ammonia and hydrogen respectively.
The electrolyte in the step (1) is 0.3-0.6M ammonium sulfate solution or 0.05-0.15M sodium sulfate solution. The pH value of the electrolyte is adjusted to 5.5-6.5 by adding sulfuric acid solution into the electrolyte solution. Introducing nitrogen into the ammonia separating cathode, and electrolyzing to prepare ammonia. Wherein the purity of the nitrogen is more than 98 percent. The electrode reaction of the ammonia-separating cathode during the electrolytic preparation of ammonia gas is as follows: n (N) 2 +6H + +6e - →2NH 3 The method comprises the steps of carrying out a first treatment on the surface of the The electrode reaction of the oxygen evolution anode is as follows:the ammonia-separating cathode is one of layered double metal hydroxide, cobalt-based catalyst, metal nitrogen doped porous carbon composite catalyst, metal phosphide, metal oxide, molten iron catalyst, molybdenum-based composite material or tungsten-based composite material, the oxygen-separating anode is NiFe-LDH, and the oxygen-separating anode can also be binary or ternary alloy catalyst of transition metal, wherein the alloy is a combination of nickel, iron and cobalt; a transition metal hydroxide catalyst; a transition metal oxide catalyst; a transition metal sulfide catalyst; a transition metal phosphide catalyst; transition metals include, but are not limited to, nickel, iron, cobalt.
In the electrolytic ammonia production process, ammonia gas generated at the ammonia-separating cathode is easily combined into ammonium ions existing in the electrolyte because the solution is acidic. At this time, an alkaline solution is added to the electrolyte to adjust the pH of the electrolyte to 13-14, while the electrolyte solution is heated to 70-90℃by a heater. The alkaline solution is added to avoid ammonia gas generated by electrolysis to exist in the electrolyte solution, and the pH value of the electrolyte solution can be adjusted to be alkaline to prepare for water electrolysis under alkaline conditions. The electrolyte solution is heated to 70-90 ℃ so that ammonia gas is easier to release, meanwhile, the temperature of conventional water electrolysis hydrogen production is reached, the electrolyte is not required to be heated again during hydrogen production, and the energy consumption is reduced. The alkaline solution may be a 20% -40% potassium hydroxide solution or a 20% -30% sodium hydroxide solution by mass, it being understood that the alkaline solution may also be other suitable alkaline solutions. In addition, when the electrolyte is an ammonium sulfate solution, ammonia gas generated by the ammonia-separating cathode and ammonium ions are contained in the electrolyte solution, and in the acidic electrolyte, the ammonium ions are changed into the ammonia gas to overflow in the subsequent pH adjusting process, so that more ammonia gas can be collected when the concentration of the ammonium ions in the solution is high. The electrolyte may be heated by electric heating or solar heating.
After collecting ammonia, changing the electrifying mode, preparing hydrogen by electrolysis under alkaline condition, and collecting hydrogen at a hydrogen evolution cathode. Changing the energizing mode is to change the energizing mode from the electrolytic ammonia production working area to the electrolytic hydrogen production working area. The electrode reaction of the hydrogen evolution cathode during the preparation of hydrogen by electrolysis is as follows: 4H (4H) 2 O+4e - →2H 2 ↑+4OH - The method comprises the steps of carrying out a first treatment on the surface of the The electrode reaction of the oxygen evolution anode is as follows: 4OH - -4e - →2H 2 O+O 2 And ≡. It can be seen that oxygen is always generated at the oxygen evolving anode during the whole electrolysis process, so that oxygen is collected at the oxygen evolving anode and stored for later use. The hydrogen evolution cathode is a nickel-molybdenum alloy, molybdenum sulfide, metal phosphide, metal oxide, metal sulfide or multi-element alloy electrode, wherein when the hydrogen evolution cathode is a multi-element alloy electrode, the alloy components can be platinum, tungsten, rhodium, nickel, molybdenum, cobalt, iron, bismuth, chromium and other elements. The types of the electrodes of the ammonia-separating cathode and the hydrogen-separating cathode are different, and the electrolytic tank is divided into an ammonia-producing working area and a hydrogen-producing working area, so that the efficiency can be improved.
After the hydrogen preparation process is finished, if the electrolysis is needed to prepare ammonia, the pH value of the electrolyte is adjusted to 5.5-6.5, and the electrifying mode is changed to be switched to an ammonia preparation working area. It will be appreciated that ammonia gas or hydrogen gas may be selectively produced according to actual needs.
As shown in fig. 1, the ammonia-making hydrogen production dual-functional electrolysis system of the invention comprises an ammonia-separating cathode 1, a hydrogen-separating cathode 2, an oxygen-separating anode, a heater 8 and a pH meter 4.
When ammonia is needed to be prepared, the ammonia-separating cathode 1 and the oxygen-separating anode 3 are electrified, and the ammonia-preparing working area works. Pumping acid solution into the electrolyte to adjust the pH value of the electrolyte to 5.5-6.5, introducing nitrogen into the ammonia separating cathode 1, and electrolyzing to prepare ammonia. Wherein the acidic solution is stored in an acidic solution storage tank 10.
Pumping alkaline solution into the electrolyte to adjust the pH value of the electrolyte to 13-14, starting a heater 8 to heat the electrolyte to 70-90 ℃, collecting separated ammonia gas, and collecting the ammonia gas generated by electrolysis at the ammonia separation cathode 1 into an ammonia storage tank 5. Wherein the alkaline solution is stored in an alkaline solution storage tank 9.
And changing the electrifying mode to electrify the hydrogen evolution cathode 2 and the oxygen evolution anode 3, and operating the hydrogen production working area. Hydrogen is prepared by electrolysis, and the hydrogen generated by electrolysis at the hydrogen evolution cathode 2 is collected in a hydrogen storage tank 6. In addition, during the electrolysis process, oxygen generated by electrolysis at the oxygen evolving anode 3 is collected in the oxygen storage tank 7.
The pH meter 4 is used to measure the pH value of the electrolyte.
It will be appreciated that in the actual production process, the ammonia production work zone and the hydrogen production work zone may be switched to produce ammonia and hydrogen as required.
Example 1:
the ammonia-separating cathode is Fe 2 O 3 Nanometer ammonia producing catalyst with hydrogen evolving cathode MoS 2 The oxygen-evolving anode is Ni 0.69 Co 0.31 -P, electrolyte is a solution of 0.05M sodium sulphate, alkaline solution is 25% koh solution by mass and acidic solution is 80% sulfuric acid solution by mass.
Regulating the pH value of the electrolyte to 5.5, introducing nitrogen with the purity of 99% into an ammonia separating cathode, and electrolyzing to prepare ammonia; regulating the pH value of the electrolyte to 13, heating the electrolyte to 80 ℃, and collecting ammonia gas; changing the power-on mode, preparing hydrogen by electrolysis, and collecting hydrogen at a hydrogen evolution cathode.
Example 2:
the ammonia-separating cathode is cobalt phosphide hollow nano-cage catalyst, the hydrogen-separating cathode is CoNi-OOH, the oxygen-separating anode is NiFe-LDH/CNT, the electrolyte is 0.5M ammonium sulfate solution, the alkaline solution is 30% KOH solution by mass fraction, and the acidic solution is 85% sulfuric acid solution by mass fraction.
Regulating the pH value of the electrolyte to 5.7, introducing nitrogen with the purity of 99% into an ammonia separating cathode, and electrolyzing to prepare ammonia; regulating the pH value of the electrolyte to 13.1, heating the electrolyte to 83 ℃, and collecting ammonia gas; changing the power-on mode, preparing hydrogen by electrolysis, and collecting hydrogen at a hydrogen evolution cathode.
Example 3:
the ammonia-separating cathode is metal carbide catalyst Mo 2 TiC 2 The hydrogen evolution anode is S-MoP, the oxygen evolution anode is NiCoFeS/NF, the electrolyte is 0.1M sodium sulfate solution, the alkaline solution is 20% NaOH solution by mass, and the acidic solution is 90% sulfuric acid solution by mass.
Regulating the pH value of the electrolyte to 5.9, introducing nitrogen with the purity of 99% into an ammonia separating cathode, and electrolyzing to prepare ammonia; regulating the pH value of the electrolyte to 13.5, heating the electrolyte to 86 ℃, and collecting ammonia gas; changing the power-on mode, preparing hydrogen by electrolysis, and collecting hydrogen at a hydrogen evolution cathode.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms may be directed to different embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the spirit and principles of the invention, the scope of which is defined by the claims and their equivalents.
Claims (8)
1. The double-function electrolysis method for producing ammonia and hydrogen is characterized by comprising the following steps:
(1) Regulating the pH value of the electrolyte to be 5.5-6.5, introducing nitrogen into an ammonia separating cathode, and electrolyzing to prepare ammonia, wherein the regulation of the pH value of the electrolyte to be 5.5-6.5 is realized by adding 80-98% sulfuric acid solution into the electrolyte;
(2) The pH value of the electrolyte is adjusted to 13-14, the electrolyte is heated to 70-90 ℃, ammonia gas is collected, and the pH value of the electrolyte is adjusted to 13-14 by adding 20-40% of potassium hydroxide solution or 20-30% of sodium hydroxide solution into the electrolyte solution;
(3) Changing the power-on mode, preparing hydrogen by electrolysis, and collecting hydrogen at a hydrogen evolution cathode;
(4) And (5) repeating the steps (1) - (3) to prepare ammonia and hydrogen respectively.
2. The method of claim 1, wherein the electrolyte is a 0.3-0.6M ammonium sulfate solution or a 0.05-0.15M sodium sulfate solution.
3. The method of claim 1, wherein the ammonia-evolving cathode is one of a layered double metal hydroxide, a cobalt-based catalyst, a metal nitrogen doped porous carbon composite catalyst, a metal phosphide, a metal oxide, a molten iron catalyst, a molybdenum-based composite material, or a tungsten-based composite material.
4. The method of claim 1, wherein the hydrogen evolution cathode is one of a nickel molybdenum alloy, molybdenum sulfide, metal phosphide, metal oxide, metal sulfide, or multi-alloy electrode.
5. The method of claim 1, wherein the nitrogen has a purity of greater than 98%.
6. The method of claim 1, wherein oxygen is collected at an oxygen evolving anode during electrolysis.
7. The method of claim 6, wherein the oxygen evolving anode is one of a NiFe-LDH, a transition metal hydroxide catalyst, a transition metal oxide catalyst, a transition metal sulfide catalyst, a transition metal phosphide catalyst, or a binary/ternary alloy catalyst of a transition metal.
8. A dual function electrolysis system for producing ammonia and hydrogen, for carrying out the method of any one of claims 1-7, comprising:
an ammonia gas generated by electrolysis at the ammonia precipitation cathode is collected into an ammonia storage tank;
a hydrogen evolution cathode, wherein hydrogen generated by electrolysis at the hydrogen evolution cathode is collected into a hydrogen storage tank;
an oxygen-separating anode, wherein oxygen generated by electrolysis at the oxygen-separating anode is collected into an oxygen storage tank, ammonia is prepared when the ammonia-separating cathode and the oxygen-separating anode are electrified, and hydrogen is prepared when the hydrogen-separating cathode and the oxygen-separating anode are electrified;
a heater for heating the electrolyte;
and a pH meter for measuring the pH value of the electrolyte.
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