CN117534122B - Conductive particle based on microscale reaction layer surface and used for hydrogen production by water electrolysis and application - Google Patents
Conductive particle based on microscale reaction layer surface and used for hydrogen production by water electrolysis and application Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000001257 hydrogen Substances 0.000 title claims abstract description 98
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 54
- 239000002245 particle Substances 0.000 title claims abstract description 54
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title abstract description 49
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 57
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 29
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 29
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 25
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 16
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 16
- 239000011592 zinc chloride Substances 0.000 claims description 16
- 235000005074 zinc chloride Nutrition 0.000 claims description 16
- 239000000498 cooling water Substances 0.000 claims description 15
- 150000003841 chloride salts Chemical class 0.000 claims description 14
- 229960003280 cupric chloride Drugs 0.000 claims description 13
- 235000010265 sodium sulphite Nutrition 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000006249 magnetic particle Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 230000005684 electric field Effects 0.000 abstract description 4
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000011010 flushing procedure Methods 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 150000001804 chlorine Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention belongs to the field of high-efficiency electrolytic hydrogen production, and provides conductive particles based on a microscale reaction layer and used for water electrolysis hydrogen production and application thereof, wherein the conductive particles comprise: the micro-fluidic reaction unit and the magnetic micron conductive particles are stably adsorbed in the micro-channel to form a stable magnetic field. The conductive particles of the invention are adopted to electrolyze water to prepare hydrogen in a micro-scale magnetic environment, so that the purity of the hydrogen can be improved, the power consumption of the hydrogen can be reduced, and the safety of the hydrogen preparation process can be improved. The invention strengthens the electrolysis effect of the electric field by utilizing the microscale magnetic environment, improves the utilization efficiency of electric energy and reduces the generation of heat, thereby not only obtaining excellent hydrogen production efficiency, but also obtaining a safe water electrolysis hydrogen production process. The invention solves the problems of safety, high efficiency and energy consumption in the hydrogen preparation process.
Description
Technical Field
The invention belongs to the technical field of high-efficiency electrolytic hydrogen production, and relates to conductive particles based on a microscale reaction layer and used for water electrolysis hydrogen production and application thereof.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Hydrogen is an important heat exchange medium of a hydrogen cooling unit, plays an indispensable role in a power plant, and simultaneously starts to be widely applied along with the gradual use of hydrogen as an important green fuel and the pressure of new energy consumption, so that the adoption of new energy electricity and garbage electricity for hydrogen production is an important technical field which needs to be developed at present, and the large-scale electrolysis hydrogen production is required to be an efficient and safe hydrogen production process, and is particularly important in areas for concentrated hydrogen production and concentrated hydrogen storage.
The electrolytic hydrogen production process is a process of electrolyzing water molecules by adopting electric energy and purifying by a hydrogen separation device, and the process firstly has the problem of intense heat during long-time working, and along with the intense heat, the electrolyte temperature is increased, so that potential safety hazards are easily caused, and the problems of corrosion, hardening and the like of an electrolytic tank are easily caused, so that the normal operation of equipment is influenced. Secondly, the electric energy utilization efficiency is low, and high-quality electric energy is adopted when an electric power generation enterprise produces hydrogen by an electrolysis method, and the electric energy utilization efficiency is lower than 50%, so that great energy waste is caused.
Therefore, under the prospect of large-scale application of hydrogen as green fuel, on one hand, the energy consumption in the hydrogen production process is reduced, the utilization efficiency of electric energy is greatly improved, low-quality electric energy is used as much as possible, and on the other hand, the heat generated in the hydrogen preparation process is timely dissipated, so that the hydrogen production method is an important technical guarantee for large-scale hydrogen production and efficient and safe hydrogen production. Solves the problems of safety, high efficiency and energy consumption in the hydrogen preparation process, and is a hot spot for research in the field.
Disclosure of Invention
Aiming at the problems of higher energy consumption, low capacity utilization rate, too fast heat production and the like in the current electrolytic hydrogen production process, the invention provides a microscale strengthening process for electrolytic hydrogen production. The invention can utilize the electric energy with lower quality, and can greatly improve the utilization rate of the electric energy, thereby reducing the preparation cost of the hydrogen and simultaneously timely radiating a large amount of heat generated in the preparation process of the hydrogen. Therefore, the invention is suitable for the preparation requirement of hydrogen in large scale.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in a first aspect of the invention, a micro-scale reaction layer-based conductive particle for producing hydrogen by water electrolysis is provided, and the conductive particle is prepared by the following method:
ferric chloride, cupric chloride and zinc chloride are mixed according to the mass ratio of 5-7:1-2:1 to 1.5, and dissolving the mixture in water to obtain a chloride salt solution;
and under the protection of inert atmosphere, adding sodium sulfite into the chloride solution, uniformly mixing, adding ammonia water for reaction, adding citric acid solution after the reaction is complete, continuing the reaction, cooling after the reaction is complete, collecting the generated magnetic particles, washing and drying to obtain the conductive particles.
Further, the mass ratio of the total mass of the ferric chloride, the cupric chloride and the zinc chloride to the water is 1:100.
further, the mass ratio of the sodium sulfite to the chloride salt solution is 1:200.
further, the mass fraction of the ammonia water is 25% -28%.
Further, the mass ratio of the ammonia water to the chloride salt solution is 1:20.
further, the citric acid solution concentration was 3%.
Further, the mass ratio of the citric acid solution to the ammonia water solution is 1:5.
more specifically, the conductive particles are prepared by the following process:
firstly, preparing composite ultra-micron conductive particles, mixing ferric chloride, cupric chloride and zinc chloride, dissolving in deionized water, adding sodium sulfite under the protection of nitrogen, stirring for 30min, quickly adding ammonia water, reacting for 1h, dropwise adding citric acid solution, continuing reacting for 1h, cooling to room temperature, sucking the prepared magnetic particles by using a magnet, and flushing with acetone and deionized water for three times respectively to obtain the ultra-micron conductive particles.
And then filling the ultra-micron conductive particles into a plurality of micro-scale reactors, wherein the ultra-micron conductive particles are adsorbed on the inner surface of the stainless steel reactor, and the micro-scale reactors are combined to form the micro-reaction unit.
In a second aspect of the present invention, there is provided the use of the above-described conductive particles in the preparation of a microreaction unit assembled by a method comprising:
and respectively filling the conductive particles prepared by the method into a plurality of microscale reactors, so that the conductive particles are adsorbed on the inner surfaces of the microscale reactors, and then communicating the microscale reactors loaded with the conductive particles to form a microreaction unit.
Further, the channel size of the microreaction unit is 15 μm to 25 μm.
The micro-reaction unit has excellent magnetism and conductivity, conductive particles can be stably adsorbed on the inner surface of the stainless steel micro-scale reactor and uniformly dispersed, so that the conduction of current can be enhanced, and the electrolysis efficiency of hydrogen production by water electrolysis is improved by reducing the electrolysis energy consumption. And no matter whether an external electric field exists or not, the micro-scale particles can be closely adhered to the inner wall of the stainless steel reactor, so that particle loss caused by the processes of flushing and the like is avoided. Meanwhile, the conductive particles have stable properties, cannot be oxidized by generated oxygen or carried air, and can stably and efficiently exert the conductive property and maintain the magnetism of the conductive particles. And the reaction scale can be controlled by controlling the input amount of the micro-reactor without adjusting other parameters, so that the method is suitable for the hydrogen production process of various modes and various scenes.
Further, 1-2 layers of ultra-micron conductive particles are adsorbed on the inner surface of the micro-scale reactor.
The number of the microscale reactors in the microscale water electrolysis unit is not particularly limited, and one skilled in the art can select the microscale reactors according to the requirement of hydrogen production in unit time.
In a third aspect, the present invention provides an application of the above conductive particles in hydrogen production by water electrolysis, including:
filling the conductive particles prepared by the method into a plurality of microscale reactors respectively, enabling the conductive particles to be adsorbed on the inner surfaces of the microscale reactors, and then communicating the microscale reactors loaded with the conductive particles to form a microreaction unit;
adding potassium hydroxide solution into the micro-reaction unit, placing the micro-reaction unit in a cooling water circulation system, switching on a power supply to generate current, generating hydrogen by a cathode, generating oxygen by an anode, separating the hydrogen from water, and collecting the hydrogen to obtain the catalyst;
and (3) maintaining the cooling water circulation in a forced circulation state during electrolysis.
Further, the temperature of the cooling water is 2-4 ℃.
Further, the electrolytic hydrogen production process comprises the following steps: the external power supply voltage is 12V-13V, and the addition amount of potassium hydroxide is 3% -4%.
More specifically, the electrolytic hydrogen production process includes:
and (3) introducing deionized water added with potassium hydroxide into a reaction unit according to the requirement of the reaction scale, placing the reaction unit in a cooling water circulation system, switching on an external power supply to generate current, generating hydrogen by a cathode and oxygen by an anode, measuring the index of the hydrogen passing through a hydrogen-water separator, and collecting the qualified hydrogen.
Wherein, measurement of hydrogen/oxygen index: the purity of the gas was measured by chromatography.
The beneficial effects of the invention are that
(1) The ultra-micron conductive particles have the effect of redistributing the electric field distribution in the microfluidic channel, so that the electric field distribution is more uniform, and the utilization efficiency of electric energy is improved fully by virtue of the reaction size of micron scale;
(2) According to the invention, the micro-scale reactor is adopted to carry out the water electrolysis hydrogen production reaction at the micro scale, so that the electric energy utilization efficiency is improved, the generated heat is obviously reduced, and meanwhile, the heat generated in the reaction process can be timely and effectively exchanged into cooling water, thereby avoiding the safety problem caused by overheating;
(3) Compared with other conductive particles, the micron-sized conductive particles prepared by the method have stable properties, cannot be oxidized by generated oxygen or brought air, can stably and efficiently exert the conductive property and keep the magnetism of the micron-sized conductive particles, better improve the purity of hydrogen and reduce the energy consumption in the hydrogen production process; meanwhile, the micron-sized conductive particles can be stably adsorbed on the inner surface of the microscale reactor, and cannot flow out along with water flow scouring;
(4) The microfluidic electrolytic hydrogen production process is stable in preparation process, and the potential safety hazard problem caused by uneven hydrogen production in the hydrogen production process is avoided;
(5) According to the hydrogen preparation process, the preparation scale is controllable, the input amount of the microfluidic unit can be adjusted at any time according to the hydrogen production requirement, and the electric energy waste is avoided.
(6) The preparation method is simple, has strong practicability and is easy to popularize.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a cross-sectional view of a microscale reactor;
the device comprises a positive electrode connecting part, a negative electrode connecting part, a chip perforation connecting hole, a microfluidic channel and a demineralized water inlet of a microscale reactor, wherein the positive electrode connecting part, the negative electrode connecting part, the chip perforation connecting hole, the microfluidic channel and the demineralized water inlet of the microscale reactor are respectively arranged in the positive electrode connecting part and the negative electrode connecting part;
FIG. 2 is an external view of a microreaction unit;
the device comprises a positive electrode, an oxygen collection tank, a negative electrode, a hydrogen collection tank, a micro-reaction unit and a desalted water inlet, wherein the positive electrode is connected with the oxygen collection tank, the negative electrode is connected with the hydrogen collection tank, and the micro-reaction unit is connected with the desalted water inlet.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention will now be described in further detail with reference to the following specific examples, which should be construed as illustrative rather than limiting.
In the following examples, the method of assembling the microreaction unit is: the ultra-micro conductive particles prepared in examples 1 to 4 and comparative examples 1 to 2 were packed into a plurality of micro-scale reactors, on the inner surfaces of which 1 layer of ultra-micro conductive particles was adsorbed, and the plurality of micro-scale reactors were combined to form a micro-scale water electrolysis unit. The size of the microfluidic reactor channels was 25 μm.
Wherein the dew point is the dew point of hydrogen, the lower the dew point, the purer the hydrogen.
Example 1
(1) The mass ratio of ferric chloride, cupric chloride and zinc chloride is 5:1:1, dissolving the mixture in deionized water to obtain a chloride salt solution, wherein the ratio of the total mass of ferric chloride, cupric chloride and zinc chloride to the mass of the deionized water is 1:100. sodium sulfite is added under the protection of nitrogen, and the mass ratio of the sodium sulfite to the chloride solution is 1:200, stirring for 30min, and then rapidly adding ammonia water, wherein the mass fraction of the ammonia water is 25%, and the mass ratio of the ammonia water to the chloride salt solution is 1:20, after reacting for 1h, dropwise adding citric acid solution, wherein the concentration of the citric acid solution is 3%, and the mass ratio of the citric acid solution to the ammonia water solution is 1:5, continuing the reaction for 1h, and maintaining the temperature of the whole reaction process at 70 ℃. And then cooling to room temperature, and sucking the prepared magnetic particles by using a magnet, and respectively flushing the magnetic particles with acetone and deionized water for three times to obtain the ultra-micron conductive particles.
(2) Taking a hydrogen production station of a Huaneng canal power plant as an implementation site, carrying out a hydrogen production experiment, and forming a micro-reaction unit by a micro-scale reactor, wherein the water inflow of the micro-reaction unit is 1L/min. Introducing deionized water added with potassium hydroxide into a reaction unit, wherein the adding amount of the potassium hydroxide is 3%, placing the micro-reaction unit in a cooling water circulation system, wherein the temperature of cooling water is 3 ℃, and the circulation water system adopts a forced circulation mode. The external power supply is connected to generate current, and the voltage of the external power supply is 12V. The cathode generates hydrogen gas, and the hydrogen gas passing through the hydrogen-water separator is collected. The oxygen generated by the anode is evacuated.
(3) Determination of Hydrogen purity by chromatography
The test results were as follows:
table 1 different process hydrogen production effects
Example 2
(1) The mass ratio of ferric chloride, cupric chloride and zinc chloride is 7:2:1.5, dissolving in deionized water to obtain a chloride salt solution, wherein the ratio of the total mass of ferric chloride, cupric chloride and zinc chloride to the mass of deionized water is 1:100. sodium sulfite is added under the protection of nitrogen, and the mass ratio of the sodium sulfite to the chloride solution is 1:200, stirring for 30min, and rapidly adding ammonia water, wherein the mass fraction of the ammonia water is 28%, and the mass ratio of the ammonia water to the chloride salt solution is 1:20, after reacting for 1h, dropwise adding citric acid solution, wherein the concentration of the citric acid solution is 3%, and the mass ratio of the citric acid solution to the ammonia water solution is 1:5, continuing the reaction for 1h, and maintaining the temperature of the whole reaction process at 70 ℃. And then cooling to room temperature, and sucking the prepared magnetic particles by using a magnet, and respectively flushing the magnetic particles with acetone and deionized water for three times to obtain the ultra-micron conductive particles.
(2) Taking a hydrogen production station of a Wacapable Texas power plant as an implementation site, carrying out a hydrogen production experiment, and forming a micro-reaction unit by a micro-scale reactor, wherein the water inflow of the micro-reaction unit is 1.5L/min. Introducing deionized water added with potassium hydroxide into a reaction unit, wherein the adding amount of the potassium hydroxide is 3%, placing the micro-reaction unit into a cooling water circulation system, wherein the temperature of cooling water is 4 ℃, and the circulation water system adopts a forced circulation mode. The external power supply is connected to generate current, and the voltage of the external power supply is 12V. The cathode generates hydrogen gas, and the hydrogen gas passing through the hydrogen-water separator is collected. The oxygen generated by the anode is evacuated.
(3) Determination of Hydrogen purity by chromatography
The test results were as follows:
TABLE 2 Hydrogen production effect by different technologies
Example 3
(1) The mass ratio of ferric chloride, cupric chloride and zinc chloride is 7:1:1.5, dissolving in deionized water to obtain a chloride salt solution, wherein the ratio of the total mass of ferric chloride, cupric chloride and zinc chloride to the mass of deionized water is 1:100. sodium sulfite is added under the protection of nitrogen, and the mass ratio of the sodium sulfite to the chloride solution is 1:200, stirring for 30min, and then rapidly adding ammonia water, wherein the mass fraction of the ammonia water is 26%, and the mass ratio of the ammonia water to the chloride salt solution is 1:20, after reacting for 1h, dropwise adding citric acid solution, wherein the concentration of the citric acid solution is 3%, and the mass ratio of the citric acid solution to the ammonia water solution is 1:5, continuing the reaction for 1h, and maintaining the temperature of the whole reaction process at 70 ℃. And then cooling to room temperature, and sucking the prepared magnetic particles by using a magnet, and respectively flushing the magnetic particles with acetone and deionized water for three times to obtain the ultra-micron conductive particles.
(2) Taking a hydrogen production station of a Wacapable Texas power plant as an implementation site, carrying out a hydrogen production experiment, and forming a micro-reaction unit by a micro-scale reactor, wherein the water inflow of the micro-reaction unit is 1.5L/min. Introducing deionized water added with potassium hydroxide into a reaction unit, wherein the adding amount of the potassium hydroxide is 3%, placing the micro-reaction unit in a cooling water circulation system, wherein the temperature of cooling water is 1 ℃, and the circulation water system adopts a forced circulation mode. The external power supply is connected to generate current, and the voltage of the external power supply is 12V. The cathode generates hydrogen gas, and the hydrogen gas passing through the hydrogen-water separator is collected. The oxygen generated by the anode is evacuated.
(3) Determination of Hydrogen purity by chromatography
The test results were as follows:
TABLE 3 Hydrogen production effect by different technologies
Example 4
(1) The mass ratio of ferric chloride, cupric chloride and zinc chloride is 5:2:1.5, after mixing, dissolving in deionized water to obtain a chloride salt solution;
wherein, the ratio of the total mass of ferric chloride, cupric chloride and zinc chloride to the mass of deionized water is 1:100.
sodium sulfite is added into the chlorine salt solution under the protection of nitrogen, and the mass ratio of the sodium sulfite to the chlorine salt solution is 1:200, stirring for 30min, and then rapidly adding ammonia water, wherein the mass fraction of the ammonia water is 27%, and the mass ratio of the ammonia water to the chloride salt solution is 1:20, after reacting for 1h, dropwise adding citric acid solution, wherein the concentration of the citric acid solution is 3%, and the mass ratio of the citric acid solution to the ammonia water solution is 1:5, continuing the reaction for 1h, and maintaining the temperature of the whole reaction process at 70 ℃. Then cooling to room temperature, sucking the prepared magnetic particles by using a magnet, and flushing the magnetic particles with acetone and deionized water for three times respectively to obtain the ultra-micron conductive particles.
(2) Taking a hydrogen production station of a Wannede power plant as an implementation site, carrying out a hydrogen production experiment, wherein the experiment is as follows:
the micro-scale reactor forms a micro-reaction unit, and the water inflow rate of the micro-reaction unit is 1L/min. Deionized water to which potassium hydroxide was added was introduced into the reaction unit in an amount of 3% by weight, and the micro-reaction unit was placed in a cooling water circulation system.
The temperature of the cooling water was 2 ℃.
The circulating water system adopts a forced circulation mode.
The external power supply is connected to generate current, and the voltage of the external power supply is 12V.
The cathode generates hydrogen gas, and the hydrogen gas passing through the hydrogen-water separator is collected. The oxygen generated by the anode is evacuated.
(3) Determination of Hydrogen purity by chromatography
The test results were as follows:
table 4 different process hydrogen production effects
Comparative example 1
The difference from example 1 is that no zinc chloride was added. The mass ratio of ferric chloride to cupric chloride is 5:2.
comparative example 2
The difference from example 1 is that no copper chloride was added. The mass ratio of the ferric chloride to the zinc chloride is 5:2.
according to the description of the embodiments 1-4, compared with a microfluidic process (without conductive particles) and a traditional electrolysis process, the micro-scale reaction-layer-based electrolytic particle-based water electrolysis-induced hydrogen production process can better improve the purity of hydrogen, reduce the dew point and remarkably reduce the energy consumption in the hydrogen production process.
As is clear from comparison of example 1 and comparative examples 1 and 2, the combination of zinc chloride, copper chloride and ferric chloride has a synergistic effect in improving the purity of hydrogen and reducing the energy consumption in the hydrogen production process, compared with the formation of ultra-micron conductive particles of zinc chloride or copper chloride alone with ferric chloride.
In summary, the invention mainly builds a process for preparing hydrogen by electrolyzing water based on a microscale magnetic environment, not only improves the purity of hydrogen by utilizing the advantages of a microscale reactor, but also reduces the consumption of electric energy in the hydrogen preparation process by utilizing the advantages of the magnetic environment, solves the problems in the traditional hydrogen preparation process that the hydrogen needs deep purification and has overhigh power consumption and the like after hydrogen preparation, and changes the electrolysis process into a microscale, thereby leading the electrolysis process to be more orderly, greatly reducing the heat generation amount of the electrolysis process and improving the safety of the hydrogen preparation process. Therefore, the invention provides a set of hydrogen electrolysis preparation process with micro-flow control and magnetic environment, which improves the purity and safety of hydrogen, reduces the electricity consumption and the generated heat in the electrolysis process, and provides important technical support for the subsequent large-scale electrolysis hydrogen production.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. The conductive particle for producing hydrogen by electrolyzing water based on the microscale reaction layer surface is characterized by being prepared by adopting the following method:
ferric chloride, cupric chloride and zinc chloride are mixed according to the mass ratio of 5-7:1-2:1 to 1.5, and dissolving the mixture in water to obtain a chloride salt solution;
adding sodium sulfite into the chloride salt solution under the protection of inert atmosphere, uniformly mixing, adding ammonia water for reaction, adding citric acid solution after the reaction is complete, continuing the reaction, cooling after the reaction is complete, collecting generated magnetic particles, washing and drying to obtain conductive particles;
the mass ratio of the sodium sulfite to the chloride solution is 1:200;
the mass fraction of the ammonia water is 25% -28%;
the mass ratio of the ammonia water to the chloride salt solution is 1:20, a step of;
the concentration of the citric acid solution is 3%;
the mass ratio of the citric acid solution to the ammonia water solution is 1:5.
2. use of the conductive particles of claim 1 for the preparation of a microreaction unit, wherein the microreaction unit is assembled by a method comprising:
and respectively filling the conductive particles into a plurality of microscale reactors, enabling the conductive particles to be adsorbed on the inner surfaces of the microscale reactors, and then communicating the microscale reactors loaded with the conductive particles to form a microreaction unit.
3. Use of the conductive particles according to claim 2 for the preparation of microreaction units, wherein the microreaction units have a channel size of 15 μm to 25 μm.
4. Use of the conductive particles of claim 1 for producing hydrogen by electrolysis of water, comprising:
filling the conductive particles into a plurality of microscale reactors respectively, enabling the conductive particles to be adsorbed on the inner surface of the microscale reactors, and then communicating the microscale reactors loaded with the conductive particles to form a microreaction unit;
adding potassium hydroxide solution into the micro-reaction unit, placing the micro-reaction unit in a cooling water circulation system, switching on a power supply to generate current, generating hydrogen by a cathode, generating oxygen by an anode, separating the hydrogen from water, and collecting the hydrogen to obtain the catalyst;
and (3) maintaining the cooling water circulation in a forced circulation state during electrolysis.
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