CN115142079A - Double functions of ammonia production and hydrogen production Electrolysis method and system - Google Patents
Double functions of ammonia production and hydrogen production Electrolysis method and system Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 239000001257 hydrogen Substances 0.000 title claims abstract description 78
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 78
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 54
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 51
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 32
- 239000001301 oxygen Substances 0.000 claims description 32
- 229910052760 oxygen Inorganic materials 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- 238000003860 storage Methods 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 150000003624 transition metals Chemical class 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- -1 transition metal sulfide Chemical class 0.000 claims description 9
- 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
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 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
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 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
- 229910001325 element 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000001588 bifunctional effect Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000009977 dual effect Effects 0.000 abstract description 2
- 239000012670 alkaline solution Substances 0.000 description 12
- 150000002431 hydrogen Chemical class 0.000 description 9
- 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
- 238000003411 electrode reaction Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 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
- 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 230000004075 alteration Effects 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
- 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
- 230000005518 electrochemistry Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 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
- 230000009467 reduction Effects 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
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—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
Abstract
The invention discloses a bifunctional electrolysis method and system for producing ammonia and hydrogen. The electrolysis method can realize the effect of dual purposes by changing the operation conditions of the electrolysis bath, and can prepare both hydrogen energy and ammonia energy. The electrolysis method of the invention heats the electrolyte when collecting ammonia gas, reaches the temperature for producing hydrogen by electrolyzing water, does not need to gradually heat the electrolyte again when producing hydrogen by electrolysis, and reduces energy consumption.
Description
Technical Field
The invention relates to the technical field of hydrogen production by electrolyzing ammonia, in particular to a dual-function 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 ammonia synthesis requires high temperature and pressure reaction conditions, resulting in a large energy consumption and carbon emission. At present, the electrocatalytic nitrogen reduction (NRR) ammonia synthesis technology with zero carbon emission characteristics has a great development prospect, and provides a new approach for green ammonia synthesis. Besides ammonia energy, hydrogen energy as a clean energy source also has the advantages of no pollution and sustainable development. At present, with the continuous increase of the installed capacity of renewable energy sources, the technology of hydrogen production through electrochemistry is mature, and the conventional alkaline electrolysis water hydrogen production technology realizes the preparation of hydrogen through an electrolytic bath device. At present, the hydrogen and ammonia gas prepared by an electrolysis method are realized in different electrolytic tanks, and the dual-function purpose of preparing hydrogen from ammonia cannot be achieved, so that a dual-function electrolytic system for preparing hydrogen from ammonia is necessary to be provided to realize the dual-purpose effect of one tank.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art.
Therefore, the invention aims to provide a dual-function electrolysis method and system for producing hydrogen from ammonia.
On one hand, the invention provides a bifunctional electrolysis method for producing hydrogen from ammonia, which comprises the following steps:
(1) Adjusting the pH value of the electrolyte to 5.5-6.5, introducing nitrogen into an ammonia-separating cathode, and electrolyzing to prepare ammonia gas;
(2) Adjusting the pH value of the electrolyte to 13-14, heating to 70-90 ℃, and collecting ammonia gas;
(3) Changing the electrifying mode, preparing hydrogen by electrolysis, and collecting the hydrogen at a hydrogen evolution cathode;
(4) And (4) repeating the steps (1) to (3) to respectively prepare ammonia gas and hydrogen gas.
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 5.5-6.5 is achieved by adding 80-98% by mass of a sulfuric acid solution to the electrolyte.
In some embodiments, adjusting the pH of the electrolyte to 13-14 is achieved 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 metallic nitrogen-doped porous carbon composite catalyst, a metallic phosphide, a metallic oxide, a molten iron catalyst, a molybdenum-based composite, or a tungsten-based composite.
In some embodiments, the hydrogen evolving cathode is one of a nickel molybdenum alloy, molybdenum sulfide, metal phosphide, metal oxide, metal sulfide, or multi-alloy electrode.
In some embodiments, the nitrogen is more than 98% pure.
In some embodiments, oxygen is collected at the oxygen evolving anode during electrolysis.
In some embodiments, the oxygen evolution 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 transition metal binary/ternary alloy catalyst.
On the other hand, the invention provides a bifunctional electrolysis system for producing ammonia and hydrogen, which comprises:
the ammonia gas generated by electrolysis at the ammonia separating cathode is collected into an ammonia storage tank;
the hydrogen generated by electrolysis at the hydrogen evolution cathode is collected into a hydrogen storage tank;
the oxygen generated by electrolysis at the oxygen evolution anode is collected into an oxygen storage tank, the ammonia evolution cathode and the oxygen evolution anode are electrified to prepare ammonia gas, and the hydrogen evolution cathode and the oxygen evolution anode are electrified to prepare hydrogen gas;
a heater for heating the electrolyte;
a pH meter is arranged on the base plate, the pH meter is used 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 dual purposes by changing the operation conditions of the electrolysis bath, and can prepare both hydrogen energy and ammonia energy.
The electrolysis method of the invention heats the electrolyte when collecting ammonia gas, reaches the temperature for electrolyzing water to produce hydrogen, does not need to gradually heat the electrolyte again when electrolyzing to produce hydrogen, and reduces energy consumption.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic diagram of a dual-function electrolysis system for producing ammonia and hydrogen;
description of reference numerals:
the device comprises 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 acidic solution storage tank 10.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are illustrative and intended to explain the present invention and should not be construed as limiting the present invention.
The dual-function electrolysis method and system for producing hydrogen from ammonia provided by the embodiment of the invention are described below with reference to the attached drawings.
The invention discloses a bifunctional electrolysis method for producing hydrogen from ammonia, which comprises the following steps:
(1) Adjusting the pH value of the electrolyte to 5.5-6.5, introducing nitrogen into an ammonia-separating cathode, and electrolyzing to prepare ammonia gas;
(2) Adjusting the pH value of the electrolyte to 13-14, heating to 70-90 ℃, and collecting ammonia gas;
(3) Changing the electrifying mode, electrolyzing to prepare hydrogen, and collecting the hydrogen at a hydrogen evolution cathode;
(4) And (4) repeating the steps (1) to (3) to respectively prepare ammonia gas and hydrogen gas.
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 a sulfuric acid solution into the electrolyte solution. And introducing nitrogen into the ammonia separating cathode to prepare ammonia gas through electrolysis. Wherein the purity of the nitrogen is more than 98 percent. The electrode reaction of the ammonia-separating cathode in the process of preparing ammonia gas by electrolysis is as follows: n is a radical of 2 +6H + +6e - →2NH 3 (ii) a The electrode reaction of the oxygen evolution anode is as follows:
the ammonia evolution cathode is one of 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, the oxygen evolution anode is NiFe-LDH, and can also be a binary or ternary alloy catalyst of transition metal, wherein the alloy is the 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.
During the process of preparing ammonia by electrolysis, ammonia gas generated by the ammonia-separating cathode is easy to combine into ammonium ions because the solution is acidic, and the ammonium ions exist in the electrolyte. At this time, an alkaline solution is added to the electrolyte to adjust the pH of the electrolyte to 13-14, and the electrolyte solution is heated to 70-90 ℃ by a heater. The alkaline solution is added to prevent ammonia gas generated by electrolysis from existing in the electrolyte solution, and the pH of the electrolyte can be adjusted to be alkaline to prepare for electrolyzing water under alkaline conditions. The electrolyte solution is heated to 70-90 ℃ so that ammonia gas is released more easily, the temperature of conventional water electrolysis hydrogen production is reached, the electrolyte does not need to be heated again during hydrogen production by electrolysis, and the energy consumption is reduced. The alkaline solution may be a 20-40% by mass potassium hydroxide solution or a 20-30% by mass sodium hydroxide solution, it being understood that the alkaline solution may also be other suitable alkaline solutions. In addition, when the electrolyte is an ammonium sulfate solution, ammonium ions are contained in the electrolyte solution, ammonia generated by an ammonia precipitation cathode can become ammonium ions in the acidic electrolyte, and the ammonium ions can become ammonia to overflow in the subsequent pH adjusting process, so that more ammonia can be collected if the concentration of the ammonium ions in the solution is high. The electrolyte can be heated by electric heating or solar heating.
After ammonia gas is collected, the electrifying mode is changed, hydrogen gas is prepared by electrolysis under the alkaline condition, and the hydrogen gas is collected at the hydrogen evolution cathode. Changing the power-on mode means that the power-on mode is changed from the electrolytic ammonia production working area to the electrolytic hydrogen production working area. The electrode reaction of the hydrogen evolution cathode when the hydrogen is prepared by electrolysis is as follows: 4H 2 O+4e - →2H 2 ↑+4OH - (ii) a The electrode reaction of the oxygen evolution anode is as follows: 4OH - -4e - →2H 2 O+O 2 ×) @. 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 ammonia separating cathode and the hydrogen separating cathode have different electrode types, and the efficiency can be improved by dividing the electrolytic cell into an ammonia production working area and a hydrogen production working area.
After the hydrogen preparation process is finished, if the ammonia gas is prepared by electrolysis, the pH value of the electrolyte is adjusted to 5.5-6.5, and the power-on mode is changed to switch to an ammonia preparation working area. It is understood that the preparation of ammonia or the preparation of hydrogen can be selected according to actual needs.
As shown in figure 1, the dual-function electrolysis system for producing hydrogen and ammonia 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 gas needs to be prepared, the ammonia separating cathode 1 and the oxygen separating anode 3 are electrified, and the ammonia preparation 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 evolution cathode 1, and electrolyzing to prepare ammonia gas. 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 temperature of the electrolyte to 70-90 ℃, collecting separated ammonia gas, and collecting the ammonia gas generated by electrolysis at an 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, so that the hydrogen production working area works. Hydrogen is prepared by electrolysis, and the hydrogen generated by the electrolysis at the hydrogen evolution cathode 2 is collected in the hydrogen storage tank 6. In addition, during the electrolysis, oxygen generated by electrolysis at the oxygen evolution anode 3 is collected in the oxygen storage tank 7.
The pH meter 4 is used for measuring the pH value of the electrolyte.
It can be understood that in the actual production process, the ammonia production working area and the hydrogen production working area can be switched according to actual needs to produce ammonia gas and hydrogen gas.
Example 1:
the ammonia-separating cathode is Fe 2 O 3 The nanometer ammonia-producing catalyst has MoS as hydrogen evolution cathode 2 The oxygen evolution anode is Ni 0.69 Co 0.31 -P, electrolyte is a 0.05M solution of sodium sulfate, alkaline solution is a KOH solution with a mass fraction of 25%, the acid solution is a sulfuric acid solution with the mass fraction of 80%.
Adjusting the pH value of the electrolyte to 5.5, introducing nitrogen with the purity of 99% into an ammonia precipitation cathode, and electrolyzing to prepare ammonia gas; adjusting the pH value of the electrolyte to 13, heating the electrolyte to 80 ℃, and collecting ammonia gas; changing the electrifying mode, electrolyzing to prepare hydrogen, and collecting the hydrogen at the hydrogen evolution cathode.
Example 2:
the ammonia-separating cathode is a cobalt phosphide hollow nano cage catalyst, the hydrogen-separating cathode is CoNi-OOH, the oxygen-separating anode is NiFe-LDH/CNT, the electrolyte is a 0.5M ammonium sulfate solution, the alkaline solution is a 30% KOH solution in mass fraction, and the acidic solution is a 85% sulfuric acid solution in mass fraction.
Adjusting the pH value of the electrolyte to 5.7, introducing nitrogen with the purity of 99% into an ammonia precipitation cathode, and electrolyzing to prepare ammonia gas; adjusting the pH value of the electrolyte to 13.1, heating the electrolyte to 83 ℃, and collecting ammonia gas; changing the electrifying mode, electrolyzing to prepare hydrogen, and collecting the hydrogen at the hydrogen evolution cathode.
Example 3:
the ammonia-separating cathode is a metal carbide catalyst Mo 2 TiC 2 The hydrogen evolution cathode is S-MoP, the oxygen evolution anode is NiCoFeS/NF, the electrolyte is 0.1M sodium sulfate solution, the alkaline solution is 20 percent NaOH solution by mass fraction, and the acidic solution is 90 percent sulfuric acid solution by mass fraction.
Adjusting the pH value of the electrolyte to 5.9, introducing nitrogen with the purity of 99% into an ammonia precipitation cathode, and electrolyzing to prepare ammonia gas; adjusting the pH value of the electrolyte to 13.5, heating the electrolyte to 86 ℃, and collecting ammonia gas; changing the electrifying mode, electrolyzing to prepare hydrogen, and collecting the hydrogen at the hydrogen evolution cathode.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean 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 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, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to implicitly indicate the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of the feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless explicitly specified otherwise.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (10)
1. The double-function electrolysis method for producing hydrogen by ammonia production is characterized by comprising the following steps:
(1) Adjusting the pH value of the electrolyte to 5.5-6.5, introducing nitrogen into an ammonia evolution cathode, and electrolyzing to prepare ammonia gas;
(2) Adjusting the pH value of the electrolyte to 13-14, heating to 70-90 ℃, and collecting ammonia gas;
(3) Changing the electrifying mode, preparing hydrogen by electrolysis, and collecting the hydrogen at a hydrogen evolution cathode;
(4) And (4) repeating the steps (1) to (3) to respectively prepare ammonia gas and hydrogen gas.
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 adjusting the pH of the electrolyte to 5.5-6.5 is performed by adding a solution of 80-98% sulfuric acid by mass to the electrolyte.
4. The method of claim 1, wherein adjusting the pH of the electrolyte to 13-14 is accomplished by adding a 20-40% by mass potassium hydroxide solution or a 20-30% by mass sodium hydroxide solution to the electrolyte solution.
5. The method of claim 1, wherein the ammonia-evolving cathode is one of a layered double hydroxide, a cobalt-based catalyst, a metallic nitrogen-doped porous carbon composite catalyst, a metallic phosphide, a metallic oxide, a molten iron catalyst, a molybdenum-based composite, or a tungsten-based composite.
6. The method of claim 1, wherein the hydrogen evolving cathode is one of a nickel molybdenum alloy, molybdenum sulfide, metal phosphide, metal oxide, metal sulfide or multi-element alloy electrode.
7. The method of claim 1, wherein the nitrogen gas has a purity of greater than 98%.
8. The method of claim 1, wherein oxygen is collected at the oxygen evolving anode during electrolysis.
9. The method of claim 8, wherein the oxygen evolving anode is one of NiFe-LDH, transition metal hydroxide catalyst, transition metal oxide catalyst, transition metal sulfide catalyst, transition metal phosphide catalyst or transition metal binary/ternary alloy catalyst.
10. A dual-function electrolysis system for producing hydrogen from ammonia, for carrying out the method according to any one of claims 1 to 9, comprising:
the ammonia gas generated by electrolysis at the ammonia separating cathode is collected into an ammonia storage tank;
the hydrogen generated by electrolysis at the hydrogen evolution cathode is collected into a hydrogen storage tank;
the oxygen generated by electrolysis at the oxygen evolution anode is collected into an oxygen storage tank, the ammonia evolution cathode and the oxygen evolution anode are electrified to prepare ammonia gas, and the hydrogen evolution cathode and the oxygen evolution anode are electrified to prepare hydrogen gas;
a heater for heating the electrolyte;
a pH meter for measuring the pH of the electrolyte.
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| JP2006045652A (en) * | 2004-08-09 | 2006-02-16 | Kenichi Machida | Hydrogen production apparatus, ammonia production apparatus, hydrogen production method and ammonia production method |
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| CN103866343A (en) * | 2014-03-25 | 2014-06-18 | 内蒙古科技大学 | Method and device for synthesizing ammonia through carrying out efficient electrocatalytic reduction on nitrogen gas at low temperature and normal pressure |
| CN111604048A (en) * | 2020-05-25 | 2020-09-01 | 浙江大学衢州研究院 | Ammonia synthesis method by electrocatalytic reduction of nitrogen and used catalyst |
| CN111701593A (en) * | 2020-07-02 | 2020-09-25 | 济南大学 | Preparation of lithium-iron layered double-metal hydroxide catalyst and application of lithium-iron layered double-metal hydroxide catalyst in electrocatalytic nitrogen reduction |
| CN112226781A (en) * | 2020-09-30 | 2021-01-15 | 湖南大学 | Device and method for generating ammonia gas from nitrogen |
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| JP2006045652A (en) * | 2004-08-09 | 2006-02-16 | Kenichi Machida | Hydrogen production apparatus, ammonia production apparatus, hydrogen production method and ammonia production method |
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| CN103866343A (en) * | 2014-03-25 | 2014-06-18 | 内蒙古科技大学 | Method and device for synthesizing ammonia through carrying out efficient electrocatalytic reduction on nitrogen gas at low temperature and normal pressure |
| CN111604048A (en) * | 2020-05-25 | 2020-09-01 | 浙江大学衢州研究院 | Ammonia synthesis method by electrocatalytic reduction of nitrogen and used catalyst |
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