CN113061918B - Hydrogen-electricity integrated device for continuous hydrogen production and application thereof - Google Patents
Hydrogen-electricity integrated device for continuous hydrogen production and application thereof Download PDFInfo
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Abstract
The invention relates to the field of hydrogen production devices, in particular to a hydrogen-electricity integrated device for continuous hydrogen production, which comprises an anode, a cathode and electrolyte, wherein the anode is a continuous feeding metal material; the cathode is a hydrogen evolution catalyst; the electrolyte is an aqueous solution containing sodium chloride; the anode, the cathode and the electrolyte participate in the reaction, the product of the reaction is magnesium hydroxide, the magnesium hydroxide is filtered by a filtering or settling device, and the filtered or settled electrolyte is recovered and injected into the reaction again; the invention provides a hydrogen-electricity integrated device for continuously producing hydrogen, which keeps the stability of hydrogen production and power generation performance, can realize continuous hydrogen production and power generation, does not need to be stopped midway, and effectively saves manpower and production cost; the invention also provides application of the hydrogen-electricity integrated device for continuous hydrogen production, which not only can generate electricity, but also can prepare high value-added products hydrogen and nano-scale magnesium hydroxide, thereby realizing effective utilization of energy.
Description
Technical Field
The invention relates to the field of hydrogen production devices, in particular to a hydrogen-electricity integrated device for continuously producing hydrogen and application thereof.
Background
The metal-water battery replaces the cathode oxygen reduction reaction of the traditional metal-dissolved oxygen battery with the water reduction hydrogen evolution reaction, not only can generate electricity, but also can effectively prepare hydrogen, and realizes hydrogen-electricity integration. Scientists successively invent lithium-water hydrogen production batteries, zinc-water hydrogen production batteries and aluminum-water hydrogen production batteries. However, the current hydrogen production system of the battery has the problems of high cost and low safety, for example, the Li-water hydrogen production battery has high cost and the lithium-water hydrogen production battery adopts an organic solvent and has safety problems, the zinc-water hydrogen production battery has low voltage and the bipolar membrane required by the zinc-water hydrogen production battery is expensive. Among the active metals, magnesium has the advantages of high electrode potential, light weight, good physical and chemical properties and low processing cost, and has been applied to anode materials of metal-dissolved oxygen seawater batteries. Therefore, the magnesium is adopted as the anode, and the magnesium water-water hydrogen production battery has the advantages of low cost, environmental friendliness and high energy utilization efficiency.
However, the existing metal-water battery device mainly adopts intermittent power generation to produce hydrogen, and in practical application, the device needs to be stopped for replacement after reaction raw materials are exhausted, so that the requirement of practical application cannot be met. Therefore, a metal-water hydrogen production battery device capable of continuously producing hydrogen needs to be designed and prepared, so that the aim of sustainable hydrogen production and power generation is fulfilled.
Disclosure of Invention
In order to solve the technical problems, the invention provides the hydrogen-electricity integrated device for continuously producing hydrogen, which keeps the stability of hydrogen production and power generation performance, can realize continuous hydrogen production and power generation, does not need to be stopped midway, and effectively saves labor and production cost.
The invention also provides the application of the hydrogen-electricity integrated device for continuously producing hydrogen, which not only can generate electricity, but also can prepare high value-added products of hydrogen and nano-scale magnesium hydroxide, thereby realizing the effective utilization of energy.
The invention adopts the following technical scheme:
a hydrogen-electricity integrated device for continuously producing hydrogen comprises an anode, a cathode and electrolyte, wherein the anode is a continuously fed metal material; the cathode is a hydrogen evolution catalyst; the electrolyte is an aqueous solution containing sodium chloride; the anode, the cathode and the electrolyte participate in the reaction, the product of the reaction is magnesium hydroxide, the magnesium hydroxide is filtered by a filtering or settling device, and the filtered or settled electrolyte is recycled and re-injected to participate in the reaction.
The technical scheme is further improved in that the continuous feeding metal material is one of a magnesium-containing metal plate or a magnesium-containing metal foil.
In a further improvement of the above technical solution, the feeding rate v of the continuous feeding metal material is 0.45 α I/ρ hk (cm/h), wherein the current of the magnesium-water hydrogen production battery is I (a), the thickness of the continuous feeding metal material is h (cm), the width of the continuous feeding metal material is k (cm), and the density is ρ (1.7 g/cm) 3 ) The self-etching correction coefficient is α.
The technical scheme is further improved in that the self-corrosion correction coefficient alpha is 1.1-2.
The technical proposal is further improved in that the feeding speed of the continuous feeding metal material is controlled by a stepping motor.
The technical proposal is further improved in that the hydrogen evolution catalyst is at least one of platinum, platinum carbon, nickel-based catalyst and molybdenum sulfide-based catalyst.
The technical proposal is further improved in that the electrolyte is one of seawater or neutral to alkalescent aqueous solution containing sodium chloride.
The technical scheme is further improved in that the concentration of sodium chloride in the electrolyte is 0.5-3 mol/L, and the pH range is 6-12.
The technical proposal is further improved in that NH is added into the electrolyte 4 Cl，NH 4 The concentration of Cl is 0.01-0.2 mol/L.
The technical scheme is further improved in that the hydrogen-electricity integrated device for continuously producing hydrogen can adjust the hydrogen production speed and the power generation power through an external load or an electric storage device so as to meet the requirements of different application scenes.
The application of the hydrogen-electricity integrated device for continuously producing hydrogen is applied to metal-water hydrogen production batteries.
The invention has the beneficial effects that:
on the first hand, magnesium hydroxide which is a magnesium anode reaction product in the magnesium-water system gradually settles along with the reaction and is the only solid substance in the electrolyte, the electrolyte can be separated out and recycled through a filtering or settling mode, and meanwhile, the electrolyte is replenished in real time, so that the fluctuation of the components of the electrolyte is reduced, and the stability of the hydrogen production and power generation performance is maintained; in the second aspect, continuous hydrogen production and power generation can be realized by continuously providing the magnesium anode without stopping the generator midway, so that manpower and production cost are effectively saved; and in the third aspect, compared with the existing magnesium-oxygen battery system, the power generation can be realized, and high value-added products, namely hydrogen and nanoscale magnesium hydroxide can be prepared, so that the effective utilization of energy is realized.
Drawings
FIG. 1 is a schematic diagram of a hydrogen-electricity integrated apparatus for continuous hydrogen production according to the present invention;
FIG. 2 is a graph showing the hydrogen production rate of the hydrogen-electricity integrated device for continuously producing hydrogen according to the present invention as a function of time.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the present invention.
A hydrogen-electricity integrated device for continuously producing hydrogen comprises an anode, a cathode and electrolyte, wherein the anode is a continuously fed metal material; the cathode is a hydrogen evolution catalyst; the electrolyte is an aqueous solution containing sodium chloride; the anode, the cathode and the electrolyte participate in the reaction, the reaction product is magnesium hydroxide, the magnesium hydroxide is filtered by a filtering or settling device, and the filtered or settled electrolyte is recycled and re-injected to participate in the reaction.
The continuous feeding metal material is one of a magnesium-containing metal plate or a magnesium-containing metal foil.
The feeding speed v of the continuous feeding metal material is 0.45 alpha I/rho hk (centimeter per hour), wherein the current of the magnesium-water hydrogen production battery is I (A), the thickness of the continuous feeding metal material is h (centimeter), the width of the continuous feeding metal material is k (centimeter), and the density is rho (1.7 g/centimeter) 3 ) The self-corrosion correction coefficient is alpha; the self-corrosion correction coefficient alpha is 1.1-2.
The feed rate of the continuously fed metal material is related to the current of the hydrogen-producing cell, and the theoretical feed rate (cm/hr) of the magnesium-containing metal sheet or foil is:
v＝I x 3600/F/2x 24.3/ρ/h/k
＝0.45I/ρhk
wherein the continuous feed metal material has a thickness of h (cm), a width of k (cm), and a density of ρ (-1.7 g/cm) 3 ) The magnesium-water hydrogen production battery has the current I (A) and the Faraday constant F (96485 coulomb/mol)
Further, because magnesium has a self-corrosion phenomenon, in actual operation, the feeding rate needs to be multiplied by a correction coefficient alpha (1.1-2) according to the self-corrosion actual condition of the continuous feeding metal material, namely the actual feeding rate is as follows:
v＝0.45αI/ρhk
the feeding rate of the continuous feeding metal material is controlled by a stepping motor, and the continuous hydrogen production power generation is realized by feeding at the rate.
The hydrogen evolution catalyst is at least one of platinum, platinum carbon, a nickel-based catalyst and a molybdenum sulfide-based catalyst.
The electrolyte is one of seawater or neutral to weakly alkaline aqueous solution containing sodium chloride.
The concentration of sodium chloride in the electrolyte is 0.5-3 mol/L, and the pH range is 6-12.
The hydrogen-electricity integrated device for continuously producing hydrogen can adjust the hydrogen production speed and the power generation power by externally connecting a load or an electric storage device so as to meet the requirements of different application scenes.
The application of the hydrogen-electricity integrated device for continuously producing hydrogen is applied to metal-water hydrogen production batteries.
Fig. 1 is a schematic diagram of a hydrogen-electricity integrated device for continuously producing hydrogen, which comprises a magnesium metal material plate/foil continuous feeding anode, a hydrogen evolution cathode, a sodium chloride-based electrolyte supply system, a reaction liquid filtering, settling and recovering system, an electric energy storage and current regulation system, and a hydrogen gas collection and storage cabin. As a hydrogen production device, sodium chloride-based electrolyte is injected into an electrolytic cell, and after a circuit is connected, the electrolytic cell can start to continuously provide electric energy and simultaneously prepare hydrogen and nano-scale magnesium hydroxide.
Example 1
Using an AZ31B magnesium alloy plate as an anode, a carbon cloth loaded Pt/C as a hydrogen evolution cathode, 1mol/L NaCl +0.02mol/L NH 4 Cl solution as electrolyte, 15mA/cm 2 The current discharge of (3) produces hydrogen. During the long-time discharge hydrogen production process, the hydrogen production rate of the cell is shown in fig. 2, and no obvious change in the hydrogen production rate can be seen.
Example 2
An AZ31B magnesium alloy plate is used as an anode, a carbon cloth loaded Pt/C is used as a hydrogen evolution cathode, 1mol/L NaCl solution is used as electrolyte, and 20mA/cm is used 2 The current discharge of (3) produces hydrogen. The thickness of the AZ31B magnesium alloy plate is 0.1 cm, the width is 10 cm, the feeding rate of the magnesium alloy plate is 0.066 cm/h (the correction coefficient alpha is 1.25), and continuous hydrogen production and power generation can be realized.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the present invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (8)
1. A hydrogen-electricity integrated device for continuously producing hydrogen comprises an anode, a cathode and electrolyte, and is characterized in that the anode is a continuous feeding metal material; the cathode is a hydrogen evolution catalyst; the electrolyte is an aqueous solution containing sodium chloride; the anode, the cathode and the electrolyte participate in the reaction, the product of the reaction is magnesium hydroxide, the magnesium hydroxide is filtered by a filtering or settling device, and the filtered or settled electrolyte is recovered and injected into the reaction again;
the feeding speed v of the continuous feeding metal material is 0.45 alpha I/rho hk, the unit of the feeding speed is centimeter per hour, wherein the current of the magnesium-water hydrogen production battery is I, and the unit of the current is A; the thickness of the continuous feeding metal material is h, and the thickness unit is centimeter; continuousThe width of the formula feeding metal material is k, and the width unit is centimeter; density is rho, density unit is 1.7 g/cm 3 (ii) a The self-corrosion correction coefficient is alpha;
the self-corrosion correction coefficient alpha is 1.1-2.
2. A hydrogen-electricity integrated apparatus for continuously producing hydrogen according to claim 1, characterized in that the continuously fed metal material is one of a magnesium-containing metal plate or a magnesium-containing metal foil.
3. A hydrogen-electricity integrated apparatus for continuously producing hydrogen according to claim 1, characterized in that the feeding rate of the continuously fed metal material is controlled by a stepping motor.
4. The hydrogen-electricity integrated device for continuously producing hydrogen according to claim 1, wherein the hydrogen evolution catalyst is at least one of platinum, platinum-carbon, nickel-based catalyst and molybdenum sulfide-based catalyst.
5. A hydrogen-electricity integration apparatus for continuously producing hydrogen according to claim 1, wherein the electrolyte is one of seawater and a neutral to weakly alkaline aqueous solution containing sodium chloride.
6. A hydrogen-electricity integrated device for continuously producing hydrogen according to claim 5, characterized in that the concentration of sodium chloride in the electrolyte is 0.5-3 mol/L, and the pH range is 6-12.
7. The hydrogen-electricity integrated device for continuously producing hydrogen according to claim 1, characterized in that the hydrogen production speed and the power generation power of the hydrogen-electricity integrated device for continuously producing hydrogen are adjusted by externally connecting a load or an electric storage device, so as to meet the requirements of different application scenarios.
8. The application of the hydrogen-electricity integrated device for continuously producing hydrogen is characterized in that the hydrogen-electricity integrated device for continuously producing hydrogen as claimed in any one of claims 1 to 7 is used in a metal-water hydrogen production battery.
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| CN106882824A (en) * | 2015-12-16 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of nano-sized magnesium hydroxide preparation method and nano-sized magnesium hydroxide |
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| CN111584980A (en) * | 2020-05-27 | 2020-08-25 | 中国科学院重庆绿色智能技术研究院 | Method for recycling phosphorus resources and electric energy in urine based on magnesium air fuel cell |
| CN112501640A (en) * | 2020-12-10 | 2021-03-16 | 东莞理工学院 | Battery system for converting nitrate wastewater into ammonia |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1280714A (en) * | 1997-10-06 | 2001-01-17 | 里维奥公司 | Metal-air fuel cell battery systems employing moving anode and cathode structures |
| CN103979488A (en) * | 2013-02-07 | 2014-08-13 | 北京华泰天成科技发展有限公司 | Technology using magnesium metal for continuous hydrogen and magnesium hydroxide production |
| CN107112512A (en) * | 2014-11-13 | 2017-08-29 | 巴斯夫公司 | Electrolyte and metal hydride battery |
| CN106882824A (en) * | 2015-12-16 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of nano-sized magnesium hydroxide preparation method and nano-sized magnesium hydroxide |
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