CN113745561A - Device and method for removing hydrogen from mine hydrogen fuel cell automobile exhaust - Google Patents

Device and method for removing hydrogen from mine hydrogen fuel cell automobile exhaust Download PDF

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Publication number
CN113745561A
CN113745561A CN202110931893.1A CN202110931893A CN113745561A CN 113745561 A CN113745561 A CN 113745561A CN 202110931893 A CN202110931893 A CN 202110931893A CN 113745561 A CN113745561 A CN 113745561A
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hydrogen
layer
catalytic
automobile exhaust
pipeline
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CN113745561B (en
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张亦凡
王海军
刘少权
王洪磊
朱伟
任道远
李中南
沈泽南
许强
刘博琰
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China Coal Research Institute CCRI
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China Coal Research Institute CCRI
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0258—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the configuration of channels, e.g. by the flow field of the reactant or coolant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/0267—Collectors; Separators, e.g. bipolar separators; Interconnectors having heating or cooling means, e.g. heaters or coolant flow channels
    • 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
    • Y02E60/50—Fuel cells

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  • Manufacturing & Machinery (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

The application provides a mine hydrogen fuel cell automobile exhaust dehydrogenation device, which comprises a catalytic pipeline, wherein automobile exhaust is introduced into the catalytic pipeline; the outer layer of the catalytic pipeline is of a net structure, the inner layer of the catalytic pipeline is provided with an ion transmission interface membrane, and the outer part of the catalytic pipeline is immersed in water so that the water passes through the net structure and is connected with the ion transmission interface membrane; the ion transmission interface film comprises an ion migration layer, and a hydrogen molecule adsorption layer and a hydrolysis layer which are compounded on two opposite surfaces of the ion migration layer, and water for soaking the catalytic pipeline passes through the net structure and is connected with the hydrolysis layer. On the basis of an ion transmission interface membrane catalysis technology, the novel loop membrane interface catalytic oxidation device is designed, waste heat of a fuel cell stack is used as a catalytic heat source, and low-concentration hydrogen in tail gas is efficiently and thoroughly removed. The method has the advantages of simple structure, thorough hydrogen removal, wide application range and no extra energy consumption, and is suitable for popularization and application of the hydrogen fuel cell automobile in the underground and the aboveground closed space.

Description

Device and method for removing hydrogen from mine hydrogen fuel cell automobile exhaust
Technical Field
The application relates to the technical field of electrochemical material surface catalysis, in particular to a device and a method for removing hydrogen from automobile exhaust of a mine hydrogen fuel cell.
Background
The trackless auxiliary transport vehicle under the coal mine is the largest automobile application field in the field of underground mining, the trackless auxiliary transport vehicles commonly used at present are diesel automobiles and lithium iron phosphate electric automobiles, and the two types of automobiles have serious defects. The diesel vehicle can not be fully combusted to produce a large amount of CO and SO2And NOxThe discharge of these gases in the downhole enclosed space causes serious pollution, limiting the life safety and normal safe production of miners. The lithium iron phosphate electric automobile has long charging time and cannot work continuously, and in addition, the lithium iron phosphate battery has large weight and usually occupies more than half of the dead weight of the automobile, so that the serious waste of power is caused.
Under the large background of national carbon peak reaching and carbon neutralization policies, the hydrogen fuel cell automobile is a new energy automobile which is greatly developed in China in recent years. The hydrogen fuel cell automobile has the advantages of quick energy charging, no harmful gas emission, light dead weight of the electric pile and the fuel and the like, and has great potential in the aspect of using well and mine auxiliary transportation vehicles. The biggest limitation of the popularization and application of the hydrogen fuel cell automobile in the underground is that hydrogen leaked by each system is accumulated in a dead zone of a coal mine roof, and when the concentration exceeds the explosion limit, danger is easily caused. The hydrogen micro-leakage of the gas storage device, the pipeline and the pile part can be prevented from leaking underground by designing a sealing explosion-proof shell and emptying the gas on the well, however, the hydrogen treatment of insufficient combustion in tail gas is an important problem to be solved urgently.
The existing dehydrogenation technology for the automobile exhaust of the hydrogen fuel cell mainly comprises high-temperature oxidation combustion, electrically-driven multi-stage catalytic oxidation and the like. For example, chinese patent document CN112397753A discloses a high-temperature oxidation combustion technology for hydrogen in fuel cell exhaust. According to the technology, hydrogen is stored through a tail gas hydrogen collecting mechanism and then is sent to a combustion chamber for combustion treatment. The low-concentration hydrogen screening and storing mechanism used in the method is complex in design, hydrogen mostly escapes, the combustion chamber needs additional energy supply, and in addition, the high-temperature environment of the combustion chamber is not beneficial to further heat dissipation of the fuel cell stack. Chinese patent document CN112072147A discloses a multi-stage catalytic oxidation technology for fuel cell tail gas. The technology achieves the purpose of quickly consuming hydrogen by designing a catalytic cell assembly, forming a plurality of gas channels by a membrane electrode according to a mode of staggered sequencing of an anode and a cathode, arranging a load device between the anode of one gas channel and the cathode of the other gas channel and arranging the structure of the plurality of layers of gas channels. The method needs multi-stage complex electrode connection and a complex multi-stage catalytic oxidation layer, and needs complex pipeline connection between each stage, and moreover, the method uses an additional circuit as a key link of hydrogen catalysis, and cannot form a simple-structure and high-efficiency processing mode. Therefore, how to realize simple, efficient and low-energy-consumption treatment is an important problem of hydrogen removal of tail gas of the downhole hydrogen fuel cell.
The ion transmission interface membrane catalysis technology is a novel membrane separation technology developed in recent years. The technique employs electrons and O at the interface2The catalyst is an ion transmission medium, and realizes the catalytic oxidation of hydrogen molecules under extremely low hydrogen concentration through the synchronous coupling effect of water decomposition reaction and hydrogen oxidation reaction. The metal oxide coating with hydrogen molecule adsorption capacity and electron migration is deposited on the ion transmission interface film by an electrochemical surface treatment technology, so that the low-concentration hydrogen is thoroughly separated.
Disclosure of Invention
The present application is directed to solving, at least to some extent, one of the technical problems in the related art.
Therefore, the application aims to provide a device and a method for removing hydrogen from automobile exhaust gas of a mine hydrogen fuel cell, and on the basis of an ion transmission interface membrane catalysis technology, a novel loop membrane interface catalytic oxidation device is designed, and waste heat of a fuel cell stack is used as a catalytic heat source, so that low-concentration hydrogen in the exhaust gas can be efficiently and thoroughly removed. The method has the advantages of simple structure, thorough hydrogen removal, wide application range and no extra energy consumption, and is suitable for popularization and application of the hydrogen fuel cell automobile in the underground and the aboveground closed space.
In order to achieve the above object, the present application provides a hydrogen removal device for mine hydrogen fuel cell automobile exhaust, including:
the catalytic pipeline is filled with automobile exhaust;
the outer layer of the catalytic pipeline is of a net structure, the inner layer of the catalytic pipeline is provided with an ion transmission interface membrane, and the outer part of the catalytic pipeline is immersed in water so that the water passes through the net structure and is connected with the ion transmission interface membrane;
the ion transmission interface membrane comprises an ion migration layer, and a hydrogen molecule adsorption layer and a hydrolysis layer which are compounded on two opposite surfaces of the ion migration layer, wherein water for soaking the catalytic pipeline passes through the net structure and is connected with the hydrolysis layer, hydrolysis is carried out under the action of the hydrolysis layer, oxygen ions generated after hydrolysis are transmitted to the hydrogen molecule adsorption layer through the ion migration layer, and the hydrogen molecule adsorption layer absorbs low-concentration hydrogen in automobile exhaust and carries out catalytic oxidation reaction on the hydrogen molecule adsorption layer to generate water.
The heat conduction system is communicated with the catalytic pipeline and is used for introducing waste heat generated by the galvanic pile into the catalytic pipeline as energy of the catalytic oxidation and energy of ion transmission in the catalytic oxidation process.
The automobile exhaust gas purifying device further comprises a gas filtering device, wherein the gas filtering device is arranged at the inlet of the catalytic pipeline and is used for filtering particles in automobile exhaust gas; and
and the supercharging air inlet system is connected with the inlet of the catalytic pipeline, so that the automobile exhaust enters the inlet of the catalytic pipeline through the supercharging air inlet system, is filtered by the gas filtering device at the inlet and then enters the catalytic pipeline.
The hydrogen recovery system is a water tank coated outside the catalytic pipeline, the middle of the catalytic pipeline is immersed in the water tank, two ends of the catalytic pipeline extend out of the water tank, and one end of the water tank is connected with the hydrogen storage system and used for recovering the hydrogen generated in the hydrolysis process of the water in the water tank.
And the liquid collecting and discharging device is connected with the catalytic pipeline and is used for collecting water generated by the catalytic oxidation reaction of the hydrogen molecular adsorption layer.
Further, 20-30 catalytic pipelines are arranged, and the inlet of each catalytic pipeline is connected with the supercharged air inlet system.
Furthermore, the outer layer of the catalytic pipeline is a stainless steel or organic resin net structure.
Further, the preparation method of the ion transport layer comprises the following steps:
taking N, N-dimethylformamide, benzyl butyl phthalate and polyvinyl butyral, heating and stirring uniformly, and standing to obtain a solvent;
fully mixing the following raw materials in percentage by mass: 10-15 wt% of samarium oxide, 20-35 wt% of cerium oxide, 25-40 wt% of molybdenum oxide and 10-45 wt% of chromium oxide, heating in a muffle furnace for 24h, cooling to obtain a solid material, and adding the solid material into the solvent;
and (3) forming by a tape casting method, heating, cooling and washing to obtain the ion migration layer.
Further, the N, N-dimethylformamide, the benzylbutyl phthalate and the polyvinyl butyral are mixed in a volume ratio of 20:1: 6.
Further, the casting method has the molding pressure of 80MPa, and the heating process is carried out for 8 hours at 1200 ℃ under normal pressure after molding.
Further, the preparation method of the hydrogen molecule adsorption layer comprises the following steps:
dissolving 10-15 mg of palladium chloride and 5-10 mg of chloroplatinic acid in 100mL of 0.2mol/L hydrochloric acid solution, stirring, and standing to obtain a reaction solution;
sealing one surface of the ion migration layer by using silica gel, exposing and soaking the other opposite surface in the reaction solution, heating the solution to 70 ℃, and preserving heat for 4 hours to obtain a hydrogen molecule adsorption layer attached to one surface of the ion migration layer;
and washing and drying the hydrogen molecule adsorption layer attached to one surface of the ion migration layer and the ion migration layer.
Further, the preparation method of the ion transmission interface film comprises the following steps:
removing the silica gel, and depositing a layer of foam nickel by using vacuum ion plating;
dissolving 3-5 mL of hydrazine hydrate and 500-800 mg of sulfur in 50mL of ethanol, uniformly stirring, adding 500-800 mg of dodecyl ammonium bromide, and uniformly stirring and ultrasonically treating to obtain a mixed liquid;
and uniformly coating the mixed liquid on the surface of the foamed nickel, and placing the foamed nickel in a 120 ℃ oven for 24 hours to compound a hydrolysis layer on one surface of the ion migration layer so as to form the ion transmission interface film with a hydrogen molecule adsorption layer/ion migration layer/hydrolysis layer structure.
Furthermore, in the process of depositing a layer of foam by vacuum ion plating, the duty ratio of a nickel power supply is 30-50%, the voltage is 500-800V, and the deposition thickness is 30-50 μm.
A method for removing hydrogen from mine hydrogen fuel cell automobile exhaust comprises the following steps:
immersing the exterior of the catalytic tube in water;
introducing automobile exhaust into the catalytic pipeline;
the water which is used for impregnating the catalytic pipeline penetrates through the net structure of the outer layer of the catalytic pipeline, is in contact with a hydrolysis layer in the ion transmission interface membrane of the inner layer of the catalytic pipeline, is hydrolyzed under the action of the hydrolysis layer, and oxygen ions generated after hydrolysis are transmitted to a hydrogen molecule adsorption layer in the ion transmission interface membrane through an ion migration layer in the ion transmission interface membrane;
the hydrogen molecular adsorption layer absorbs low-concentration hydrogen in the automobile exhaust and carries out catalytic oxidation reaction on the absorbed hydrogen and the oxygen ions in the hydrogen molecular adsorption layer to generate water.
Further, waste heat generated by the galvanic pile is introduced into the catalytic pipeline to be used as energy for the catalytic oxidation and energy for ion transmission in the catalytic oxidation process.
Further, the method also comprises the step of recovering and storing the hydrogen generated in the hydrolysis process.
Further, collecting and discharging water generated by the catalytic oxidation reaction.
Additional aspects and advantages of the present application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the present application.
Drawings
The foregoing and/or additional aspects and advantages of the present application 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 sectional view showing a structure of a system for treating a tail gas containing a low concentration of hydrogen according to an embodiment of the present application;
FIG. 2 is a schematic diagram of an ion transport interfacial catalytic oxidation structure as set forth in another embodiment of the present application;
FIG. 3 is a surface SEM topography of a hydrogen molecule adsorbing layer of an ion transport interfacial catalytic oxidation catalytic membrane according to another embodiment of the present application;
FIG. 4 is an SEM topography of the surface of a hydrolysis layer of an ion transport interfacial catalytic oxidation catalytic membrane as set forth in another embodiment of the present application.
1. A catalytic conduit; 2. a heat conducting system; 3. a hydrogen recovery system; 4. a gas filtering device; 5. an air outlet; 6. a heat transfer conduit; 7. a liquid collection and discharge device.
Detailed Description
Reference will now be made in detail to embodiments of the present application, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are exemplary only for the purpose of explaining the present application and are not to be construed as limiting the present application. On the contrary, the embodiments of the application include all changes, modifications and equivalents coming within the spirit and terms of the claims appended hereto.
Fig. 1 is a schematic structural diagram of a mine hydrogen fuel cell automobile exhaust dehydrogenation device according to an embodiment of the application.
The utility model provides a mining hydrogen fuel cell automobile exhaust dehydrogenation device, includes catalysis pipeline 1, lets in automobile exhaust in the catalysis pipeline 1, can follow one section of catalysis pipeline 1 and let in tail gas to catalysis pipeline inside for tail gas disperses in catalysis pipeline 1's inside.
The outer layer of the catalytic pipeline 1 is of a net structure, the inner layer is provided with an ion transmission interface film 4, the catalytic pipeline 1 is externally immersed in water, namely, the whole catalytic pipeline 1 is of a cylindrical pipeline structure enclosed by the net structure, the outside of the pipeline structure is immersed in water and is connected with water, so that water can enter the catalytic pipeline 1 through net holes, meanwhile, the inner wall of the catalytic pipeline 1 is compounded with one layer of ion transmission interface film, and then the water is directly blocked by the ion transmission interface film 4 when entering the catalytic pipeline 1 through the net holes, and the water can be contacted with the ion transmission interface film 4, and the water can not enter the inside of the catalytic pipeline 1.
Further, as shown in fig. 2, 3 and 4, the ion transport interface film 4 includes an ion transport layer, and a hydrogen molecule adsorption layer and a hydrolysis layer which are compounded on the opposite surfaces of the ion transport layer, and water impregnated in the catalyst pipe passes through the mesh structure to contact the hydrolysis layer, and is hydrolyzed by the hydrolysis layer, and oxygen ions generated after the hydrolysis are transported to the ion transport layer through the ion transport layerAnd the hydrogen molecule adsorption layer absorbs low-concentration hydrogen in the automobile exhaust and performs catalytic oxidation reaction on the absorbed hydrogen and oxygen ions in the hydrogen molecule adsorption layer to generate water. Specifically, the ion transmission interface membrane 4 comprises a three-layer structure, a middle ion transfer layer, and a hydrogen molecule adsorption layer and a hydrolysis layer which are positioned at two sides of the ion transfer layer, wherein the hydrolysis layer is in contact with the catalytic pipeline 1, so that water can be connected with the hydrolysis layer, and when the water is in contact with the hydrolysis layer, the hydrolysis reaction can be carried out under the action of the hydrolysis layer to generate hydrogen and oxygen ions O2-The generated oxygen ions can pass through the ion migration layer to enter the hydrogen molecule adsorption layer, meanwhile, because the hydrogen molecule adsorption layer is positioned inside the catalytic pipeline, when tail gas is introduced into the catalytic pipeline, hydrogen with low concentration in the tail gas can be adsorbed by the hydrogen molecule adsorption layer, the hydrogen adsorbed on the hydrogen molecule adsorption layer and the oxygen ions entering the hydrogen molecule adsorption layer can perform catalytic oxidation reaction on the hydrogen molecule adsorption layer, so that the hydrogen is oxidized to generate water and free electrons, the electrons can move to the hydrolysis layer through the ion migration layer, further the charge in hydrolysis is balanced, the cyclic hydrolysis and catalytic oxidation processes are realized, the hydrogen with low concentration can be completely oxidized, the problems of hydrogen molecule adsorption, oxygen ion transmission and hydrolysis are solved and compounded layer by designing a multi-layer composite ion transmission membrane structure, and the structure is opposite to the principle of a proton exchange membrane, and a strong oxidation area is formed on the inner side of the membrane through the transmission of oxygen ions, so that low-concentration hydrogen is completely oxidized.
In an embodiment of the present application, the system further includes a heat conduction system 2, the heat conduction system 2 is communicated with the catalytic pipeline 1, and is configured to introduce waste heat generated by the stack into the catalytic pipeline 1 as energy of catalytic oxidation and energy of ion transmission in the catalytic oxidation process, no extra electric energy loss is needed, and hydrogen treatment can be achieved only by introducing multiple waste heat energy released by the fuel cell stack into the exhaust system, specifically, a heat transfer pipeline 6 is communicated among the multiple catalytic pipelines 1, and the waste heat generated by the stack enters the catalytic pipeline 1 through the heat transfer pipeline 6 to be heated.
In an embodiment of the present application, the catalytic device further includes a gas filtering device 4 and a supercharging air intake system, the gas filtering device 4 is disposed at an inlet of the catalytic pipeline 1, and is configured to filter particles in the automobile exhaust gas, and remove particles in the automobile exhaust gas, and the supercharging air intake system is connected to the inlet of the catalytic pipeline 1, so that the automobile exhaust gas enters the inlet of the catalytic pipeline 1 through the supercharging air intake system, and enters the catalytic pipeline 1 after being filtered through the gas filtering device 4 at the inlet, in addition, specifically, the catalytic pipeline 1 may be disposed with 20-30 catalytic pipelines, the inlet of each catalytic pipeline 1 is provided with the gas filtering device 4, and is also connected to the supercharging air intake system, and further, each catalytic pipeline 1 can perform sufficient catalytic oxidation reaction on hydrogen in the exhaust gas.
In an embodiment of the present application, further include hydrogen recovery system 3, hydrogen recovery system 3 is the cladding in the outside basin of catalysis pipeline 1, and the middle part submergence of catalysis pipeline 1 is in the aquatic in the basin, and the basin is stretched out at both ends, and the hydrogen storage system is connected to basin one end for with the water in the basin hydrogen that produces is retrieved in the hydrolysis process. Specifically, the water tank is set to be a one-way sealing structure, water is filled in the water tank, and a plurality of catalytic pipelines 1 are arranged by penetrating through upper and lower end covers of the water tank, so that the middle part of the catalytic pipeline 1 is immersed in the water tank, two ends of the catalytic pipeline 1 extend out of the water tank, one end of the catalytic pipeline is convenient to be directly connected with a pressurized air inlet system for leading in tail gas from one end, the other end of the catalytic pipeline 1 is used for discharging water generated by reaction in the catalytic pipeline 1, an inlet is arranged on the catalytic pipeline 1, the pressurized air inlet system is connected to the catalytic pipeline 1 after passing through the inlet, then the tail gas is led into the catalytic pipeline 1, an air outlet 5 is arranged on the water tank, hydrogen generated in the hydrolysis process of the water in the water tank enters a hydrogen storage system through the one-way air outlet for storage, the water tank further comprises a liquid collecting and discharging device 7, and the liquid collecting and discharging device 7 is connected with the catalytic pipeline 1, the water collecting device is used for collecting water generated by catalytic oxidation reaction of the hydrogen molecule adsorption layer, one ends of the catalytic pipelines 1 are connected to the liquid collecting and discharging device 7, and water generated by catalytic action in the catalytic pipelines 7 is conveniently and directly collected and discharged into the liquid collecting and discharging device 7.
In one embodiment of the present application, the outer layer of the catalytic tube 1 is a stainless steel mesh structure.
In one embodiment of the present application, the ion transport interface film 4 includes a three-layer structure, and during the preparation of the ion transport interface film 4, an intermediate ion transport layer is first prepared, wherein the ion transport layer is prepared by the following method:
heating 100mL of DMF (N, N-dimethylformamide), 5mL of BBP (benzylbutyl phthalate) and 30mL of PVB (polyvinyl butyral) to 65 ℃, stirring, fully mixing, and standing for 24 h;
fully mixing the following raw materials in percentage by mass: 10-15 wt% of samarium oxide, 20-35 wt% of cerium oxide, 25-40 wt% of molybdenum oxide and 10-45 wt% of chromium oxide, then heating the materials in a muffle furnace to 950 ℃, treating the materials for 24 hours, cooling the materials to obtain a solid material, grinding the solid material into powder, and adding 150mg of the powder into a solvent;
molding by tape casting at 80MPa, and heating at 1200 deg.C under normal pressure for 8 hr. After cooling, the mixture was washed with acetone and deionized water.
In one embodiment of the present application, the hydrogen molecule adsorption layer on the ion transport layer is prepared as follows:
dissolving 10-15 mg of palladium chloride and 5-10 mg of chloroplatinic acid in 100mL of 0.2mol/L hydrochloric acid solution, stirring for 15min by using an electromagnetic stirrer, and standing for 24h to obtain a reaction solution;
sealing one surface of the ion migration layer by using silica gel, exposing and soaking the other opposite surface in the reaction solution, heating the solution to 70 ℃, and preserving heat for 4 hours to obtain a hydrogen molecule adsorption layer attached to one surface of the ion migration layer;
and repeatedly washing the hydrogen molecule adsorption layer attached to one surface of the ion migration layer and the ion migration layer by using deionized water, and drying at low pressure.
In one embodiment of the present application, the ion transport interface film is prepared as follows:
removing the silica gel, depositing a layer of foam nickel by vacuum ion plating, wherein the duty ratio of a power supply is 30-50%, the voltage is 500-800V, and the deposition thickness is 30-50 mu m;
dissolving 3-5 mL of hydrazine hydrate and 500-800 mg of sulfur in 50mL of ethanol, uniformly stirring, adding 500-800 mg of dodecyl ammonium bromide, stirring for 5 hours by using an electromagnetic stirrer, and performing ultrasonic treatment for 1 hour at the frequency of 30 kHz;
and (3) uniformly coating the mixed liquid on the surface of the foamed nickel in the first step, placing the foamed nickel in a drying oven at 120 ℃ for 24 hours, taking out the foamed nickel, and wiping the foamed nickel by using absolute ethyl alcohol to clean the foamed nickel so that one surface of the ion migration layer is compounded with a hydrolysis layer to form the ion transmission interface film 4 with the structure of the hydrogen molecule adsorption layer/the ion migration layer/the hydrolysis layer.
From the above examples, it can be seen that a three-layer composite ion transport interface film having a hydrogen molecule adsorption layer/ion transport layer/hydrolysis layer structure was obtained by preparing an ion transport layer, then laminating a hydrogen molecule adsorption layer on one side of the ion transport layer, and then laminating a hydrolysis layer on the other side of the ion transport layer, and the prepared ion transport interface film had a concentration of 1000ppm of H at 200 ℃2Diffusion rate>5mL cm-2min-2Rate of electron transfer>1700cm2 V-1s-1。
In one embodiment of the application, a method for removing hydrogen from tail gas of a mine hydrogen fuel cell automobile comprises the following steps:
immersing the exterior of the catalytic tube 1 in water;
introducing automobile exhaust into the catalytic pipeline 1, filtering the exhaust through a gas filtering device 4 when the exhaust is introduced into an inlet of the catalytic pipeline 1 to remove particles in the exhaust, and then introducing the exhaust into the catalytic pipeline 1;
water dipping the catalytic pipeline 1 passes through the net structure on the outer layer of the catalytic pipeline 1, contacts with a hydrolysis layer in an ion transmission interface film on the inner layer of the catalytic pipeline 1, is hydrolyzed under the action of the hydrolysis layer, and oxygen ions generated after hydrolysis are transmitted to a hydrogen molecule adsorption layer in the ion transmission interface film 4 through an ion migration layer in the ion transmission interface film 4;
the hydrogen molecular adsorption layer absorbs low-concentration hydrogen in automobile exhaust and performs catalytic oxidation reaction on the absorbed hydrogen and oxygen ions in the hydrogen molecular adsorption layer to generate water, and the concentration of residual hydrogen in the automobile exhaust of the hydrogen fuel cell after treatment is lower than the detection limit of a common sensor (less than 1 ppm).
Further, waste heat generated by the galvanic pile is introduced into the catalytic pipeline 1 to be used as energy for catalytic oxidation and energy for ion transmission in the catalytic oxidation process.
Further, the method also comprises the step of recovering and storing the hydrogen generated in the hydrolysis process.
Further, collecting and discharging water generated by the catalytic oxidation reaction.
It should be noted that, in the description of the present application, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. In addition, in the description of the present application, "a plurality" means two or more unless otherwise specified.
Any process or method descriptions in flow charts or otherwise described herein may be understood as representing modules, segments, or portions of code which include one or more executable instructions for implementing specific logical functions or steps of the process, and the scope of the preferred embodiments of the present application includes other implementations in which functions may be executed out of order from that shown or discussed, including substantially concurrently or in reverse order, depending on the functionality involved, as would be understood by those reasonably skilled in the art of the present application.
In the description herein, reference to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," 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 application. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Although embodiments of the present application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present application, and that variations, modifications, substitutions and alterations may be made to the above embodiments by those of ordinary skill in the art within the scope of the present application.

Claims (17)

1. The utility model provides a mining hydrogen fuel cell automobile exhaust dehydrogenation device which characterized in that includes:
the catalytic pipeline is filled with automobile exhaust;
the outer layer of the catalytic pipeline is of a net structure, the inner layer of the catalytic pipeline is provided with an ion transmission interface membrane, and the outer part of the catalytic pipeline is immersed in water so that the water passes through the net structure and is connected with the ion transmission interface membrane;
the ion transmission interface membrane comprises an ion migration layer, and a hydrogen molecule adsorption layer and a hydrolysis layer which are compounded on two opposite surfaces of the ion migration layer, wherein water for soaking the catalytic pipeline passes through the net structure and is connected with the hydrolysis layer, hydrolysis is carried out under the action of the hydrolysis layer, oxygen ions generated after hydrolysis are transmitted to the hydrogen molecule adsorption layer through the ion migration layer, and the hydrogen molecule adsorption layer absorbs low-concentration hydrogen in automobile exhaust and carries out catalytic oxidation reaction on the hydrogen molecule adsorption layer to generate water.
2. The mine hydrogen fuel cell automobile exhaust hydrogen removal device according to claim 1, further comprising a heat conduction system, wherein the heat conduction system is communicated with the catalytic pipeline, and is used for introducing waste heat generated by the galvanic pile into the catalytic pipeline as energy for the catalytic oxidation and energy for ion transmission in the catalytic oxidation process.
3. The mine hydrogen fuel cell automobile exhaust dehydrogenation device according to claim 1, further comprising
The gas filtering device is arranged at the inlet of the catalytic pipeline and is used for filtering particles in the automobile exhaust; and
and the supercharging air inlet system is connected with the inlet of the catalytic pipeline, so that the automobile exhaust enters the inlet of the catalytic pipeline through the supercharging air inlet system, is filtered by the gas filtering device at the inlet and then enters the catalytic pipeline.
4. The mine hydrogen fuel cell automobile exhaust hydrogen removal device as claimed in claim 1, further comprising a hydrogen recovery system, wherein the hydrogen recovery system is a water tank coated outside the catalytic pipeline, the middle part of the catalytic pipeline is immersed in the water tank, two ends of the catalytic pipeline extend out of the water tank, and one end of the water tank is connected with a hydrogen storage system for recovering the hydrogen generated in the hydrolysis process of the water in the water tank.
5. The mine hydrogen fuel cell automobile exhaust hydrogen removal device as claimed in claim 1, further comprising a liquid collecting and discharging device connected to the catalytic pipe for collecting water generated by catalytic oxidation reaction of the hydrogen molecular adsorption layer.
6. The mining hydrogen fuel cell automobile exhaust hydrogen removal device as claimed in claim 3, wherein 20-30 catalytic pipes are arranged, and the inlet of each catalytic pipe is connected with the supercharging air intake system.
7. The mining hydrogen fuel cell automobile exhaust dehydrogenation device according to any one of claims 1-6, wherein the outer layer of the catalytic pipe is a stainless steel mesh structure.
8. The mine hydrogen fuel cell automobile exhaust dehydrogenation device according to claim 1, wherein the ion transport layer is prepared by the following method:
taking N, N-dimethylformamide, benzyl butyl phthalate and polyvinyl butyral, heating and stirring uniformly, and standing to obtain a solvent;
fully mixing the following raw materials in percentage by mass: 10-15 wt% of samarium oxide, 20-35 wt% of cerium oxide, 25-40 wt% of molybdenum oxide and 10-45 wt% of chromium oxide, heating in a muffle furnace for 24h, cooling to obtain a solid material, and adding the solid material into the solvent;
and (3) forming by a tape casting method, heating, cooling and washing to obtain the ion migration layer.
9. The mining hydrogen fuel cell automobile exhaust dehydrogenation device according to claim 8, wherein the N, N-dimethylformamide, benzylbutyl phthalate and polyvinyl butyral are mixed in a volume ratio of 20:1: 6.
10. The mine hydrogen fuel cell automobile exhaust dehydrogenation device according to claim 8,
the heating temperature in the muffle furnace is 950 ℃;
the tape casting method has the molding pressure of 80MPa, and is heated for 8 hours at the normal pressure of 1200 ℃ in the heating process after molding.
11. The mine hydrogen fuel cell automobile exhaust dehydrogenation device according to claim 1, wherein the preparation method of the hydrogen molecule adsorption layer is as follows:
dissolving 10-15 mg of palladium chloride and 5-10 mg of chloroplatinic acid in 100mL of 0.2mol/L hydrochloric acid solution, stirring, and standing to obtain a reaction solution;
sealing one surface of the ion migration layer by using silica gel, exposing and soaking the other opposite surface in the reaction solution, heating the solution to 70 ℃, and preserving heat for 4 hours to obtain a hydrogen molecule adsorption layer attached to one surface of the ion migration layer;
and washing and drying the hydrogen molecule adsorption layer attached to one surface of the ion migration layer and the ion migration layer.
12. The mine hydrogen fuel cell automobile exhaust dehydrogenation device according to claim 11, wherein the ion transmission interface membrane is prepared by the following method:
removing the silica gel, and depositing a layer of foam nickel by using vacuum ion plating;
dissolving 3-5 mL of hydrazine hydrate and 500-800 mg of sulfur in 50mL of ethanol, uniformly stirring, adding 500-800 mg of dodecyl ammonium bromide, and uniformly stirring and ultrasonically treating to obtain a mixed liquid;
and uniformly coating the mixed liquid on the surface of the foamed nickel, and placing the foamed nickel in a 120 ℃ oven for 24 hours to compound a hydrolysis layer on one surface of the ion migration layer so as to form the ion transmission interface film with a hydrogen molecule adsorption layer/ion migration layer/hydrolysis layer structure.
13. The mine hydrogen fuel cell automobile exhaust dehydrogenation device according to claim 12, wherein during the vacuum ion plating deposition of a layer of foam, the nickel power duty cycle is 30% -50%, the voltage is 500V-800V, and the deposition thickness is 30 μm-50 μm.
14. A mine hydrogen fuel cell automobile exhaust dehydrogenation method is characterized by comprising the following steps:
immersing the exterior of the catalytic tube in water;
introducing automobile exhaust into the catalytic pipeline;
the water which is used for impregnating the catalytic pipeline penetrates through the net structure of the outer layer of the catalytic pipeline, is in contact with a hydrolysis layer in the ion transmission interface membrane of the inner layer of the catalytic pipeline, is hydrolyzed under the action of the hydrolysis layer, and oxygen ions generated after hydrolysis are transmitted to a hydrogen molecule adsorption layer in the ion transmission interface membrane through an ion migration layer in the ion transmission interface membrane;
the hydrogen molecular adsorption layer absorbs low-concentration hydrogen in the automobile exhaust and carries out catalytic oxidation reaction on the absorbed hydrogen and the oxygen ions in the hydrogen molecular adsorption layer to generate water.
15. The mine hydrogen fuel cell automobile exhaust dehydrogenation device according to claim 14, further comprising: and introducing waste heat generated by the galvanic pile into the catalytic pipeline as energy of the catalytic oxidation and energy of ion transmission in the catalytic oxidation process.
16. The mine hydrogen fuel cell automobile exhaust dehydrogenation device according to claim 14, further comprising: and recovering and storing the hydrogen generated in the hydrolysis process.
17. The mine hydrogen fuel cell automobile exhaust dehydrogenation device according to claim 14, further comprising: and collecting and discharging the water generated by the catalytic oxidation reaction.
CN202110931893.1A 2021-08-13 2021-08-13 Device and method for removing hydrogen from tail gas of mine hydrogen fuel cell automobile Active CN113745561B (en)

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