CN106848336B - Preparation method and equipment of SOFC anode loaded copper-nickel bimetallic catalyst - Google Patents
Preparation method and equipment of SOFC anode loaded copper-nickel bimetallic catalyst Download PDFInfo
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- CN106848336B CN106848336B CN201611175461.8A CN201611175461A CN106848336B CN 106848336 B CN106848336 B CN 106848336B CN 201611175461 A CN201611175461 A CN 201611175461A CN 106848336 B CN106848336 B CN 106848336B
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
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- 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
Abstract
The invention relates to a method for preparing a copper-nickel bimetallic catalyst with a Solid Oxide Fuel Cell (SOFC) anode as a carrier and equipment thereof, which comprises the steps of obtaining a hydrothermal reaction precursor, fixing the obtained hydrothermal reaction precursor, the SOFC anode and a solution in a specially-made hydrothermal kettle, carrying out hydrothermal reaction to obtain a copper oxide which grows on an SOFC anode tube and is uniformly distributed and well crystallized, and then drying; placing the SOFC anode tube subjected to water heating in a muffle furnace for calcining and oxidizing to obtain the SOFC anode tube subjected to impurity removal and copper oxide on the SOFC anode tube; the SOFC anode tube after calcination was placed in a tubular furnace in a hydrogen atmosphere to perform a reduction reaction, and NiO in the SOFC anode was also reduced to Ni, so that a copper-nickel bimetallic catalyst with the SOFC anode as a carrier was obtained. The device is a special hydrothermal kettle.
Description
The technical field is as follows:
the invention belongs to the field of applied chemical engineering and energy, and relates to a preparation method of a Solid Oxide Fuel Cell (SOFC) anode supported copper and nickel bimetallic catalyst.
Background art:
in recent years, bimetallic catalysts have been actively studied in catalysis, which shows that: the activity of bimetallic catalysts is higher than that of corresponding single-component catalysts, and the selectivity of the catalysts is also greatly different. The YSZ loaded copper and nickel bimetallic catalyst used in the invention can be used as a catalyst for methanol steam reforming hydrogen production (MSR).
The Solid Oxide Fuel Cell (SOFC) is an energy conversion device which directly converts chemical energy of hydrocarbon fuel into electric energy, can properly design and transform an SOFC anode and has the function of fuel gas reforming, and hydrocarbon fuel is properly passivated and reformed to be converted into micromolecular hydrogen and carbon monoxide, so that electrochemical reaction can be smoothly carried out to generate electric energy.
The catalyst is usually prepared by impregnation, precipitation, thermal dissolution, hydrothermal method, etc. Powder with perfect crystallization and ideal grain size can be obtained through hydrothermal treatment; and compared with the hydrothermal method, the preparation process is simpler, and the SOFC anode is used as a carrier, and the hydrothermal method is used for generating copper on the carrier, so that the aim of forming uniform nano copper particles on the carrier can be fulfilled, and the catalytic effect of the carrier is enhanced.
Compared with the traditional hydrogen production method, the hydrogen production by reforming the methanol has the following 3 advantages:
(1) the hydrogen production raw material has wide source and low price, and the methanol serving as a common chemical raw material can be prepared from fossil resources and biomass;
(2) high utilization rate of hydrogen element, and the molecular formula of methanol is CH3OH, high hydrogen content, high energy density and high hydrogen yield;
(3) the hydrogen production device is simple, and the methanol is convenient to store and transport, and can be made into an assembled or movable methanol hydrogen production device.
The invention content is as follows:
the invention aims to prepare a copper-nickel bimetallic catalyst taking a Solid Oxide Fuel Cell (SOFC) anode as a carrier, which is mainly used for reforming hydrocarbon fuel and can be used as an internal reformer or an external reformer of an SOFC power generation device.
In order to realize the purpose, the invention prepares a copper-nickel bimetallic catalyst taking a Solid Oxide Fuel Cell (SOFC) anode as a carrier, and adopts the technical scheme that the preparation method comprises the following steps:
s11, placing the tubular SOFC anode tube in a reaction solution of blue copperas, formaldehyde and ammonia water for constant-temperature water bath to obtain a hydrothermal reaction precursor;
s12, fixing the hydrothermal reaction precursor, the SOFC anode and the solution obtained in the S11 in a specially-made hydrothermal kettle, carrying out hydrothermal reaction to obtain copper oxide which grows on the SOFC anode tube and is uniformly distributed and well crystallized, and drying;
s13, placing the SOFC anode tube subjected to water heating in a muffle furnace for calcining and oxidizing to obtain the SOFC anode tube subjected to impurity removal and copper oxide on the SOFC anode tube;
s14, the SOFC anode tube after firing is placed in a tube furnace in a hydrogen atmosphere to perform a reduction reaction, and NiO in the SOFC anode is also reduced to Ni, so that a copper-nickel bimetallic catalyst on the SOFC anode can be obtained.
Further, in S11, firstly, 40-100 ml of copper sulfate pentahydrate solution with the concentration of 0.5mol/L is placed in a constant temperature water bath at 60 ℃, then, tubular SOFC anode material (composed of YSZ and NiO) is put into the constant temperature water bath for 0.5-1 hour, then, 3-20 ml of formaldehyde solution and 5-70 ml of ammonia water solution are slowly dripped into the constant temperature water bath, and the water bath is continued for 0.5-2 hours, so that a hydrothermal precursor and an SOFC anode tube fully soaked by the solution are obtained.
Further, in S12, the liquid obtained in S11, the precursor, and the SOFC anode are placed in a hydrothermal reactor. And then placing the mixture into a drying oven, heating to 150-250 ℃ and reacting for 5-15 hours to obtain the hydrothermally treated SOFC anode tube.
Furthermore, the hydrothermal kettle is designed by the inventor independently and is made by a professional manufacturer, polytetrafluoroethylene in the inner container of the hydrothermal kettle is specially processed, and one of the purposes is that the inner container wall is provided with a plurality of insertion holes with the diameter of about 2mm, so that the SOFC anode tube can be stably fixed, and the porous ceramic tube is stabilized under the stirring condition; the other is that a very fine stainless steel needle penetrates into the jack and penetrates through the wall of the inner container, and a pulse voltage can be applied to the liquid in the hydrothermal kettle by using the conductor, so that the electrostatic attraction generated by the pulse voltage is utilized to increase the energy fluctuation of the area, so that copper ions are gathered around the SOFC anode tube, the number of crystal nuclei in the jack area is increased, and the top of the hydrothermal kettle is provided with a stirring device with mechanical transmission, and stirring blades of the stirring device are directly inserted below the reaction liquid level, so that the hydrothermal reaction can be carried out under the stirring condition.
In the scheme, the polytetrafluoroethylene inner container is formed by injection molding through a mold, and has excellent corrosion resistance, good self-lubricating property and non-blocking property. And after the inner container is manufactured, performing mechanical deep processing, chiseling through holes on the inner wall, and polishing corners.
In the above scheme, the pulse voltage is an intermittent discontinuous pulse.
Further, in S13, the SOFC anode tube after the hydrothermal treatment is placed into a muffle furnace, the temperature is raised to 400-700 ℃, and the heat is preserved for 0.5-2 hours, so that the SOFC anode tube after impurity removal and oxidation is obtained.
Further, in S14, adjusting a mass flow meter, controlling the flow of the hydrogen and argon mixed gas entering the vacuum tube furnace to be 10-60 sccm, setting the tube furnace to heat up to 550-900 ℃, keeping the temperature for 2-6 hours, and after the reduction reaction is finished, taking out the SOFC anode tube to obtain the copper-nickel bimetallic catalyst taking the SOFC anode as the carrier.
Description of the drawings:
FIG. 1 is a product structure diagram of a special hydrothermal kettle;
fig. 2 is an SEM picture of the copper-nickel composite catalyst obtained after the S13 step;
fig. 3 is an SEM picture of the copper-nickel composite catalyst obtained after the S14 step.
The specific embodiment is as follows:
example 1:
the preparation method of the copper-nickel bimetallic catalyst with the micro-circular tube type SOFC anode as the carrier comprises the following steps:
s11, taking 50 parts by mass of a copper sulfate pentahydrate solution, carrying out constant-temperature water bath, putting into an SOFC anode tube, sequentially adding 7 parts by mass of a formaldehyde solution and ammonia water, adjusting the pH value to 3.6, and carrying out constant-temperature water bath reaction for 30 minutes under magnetic stirring at 400RPM to obtain a mixed solution and a precursor required by a hydrothermal method;
s12, pouring the obtained SOFC anode tube, the hydrothermal precursor and the mixed solution into a customized hydrothermal kettle, putting the kettle into a drying box, heating to 240 ℃, reacting for 8 hours, and cooling to room temperature to obtain a hydrothermal product: SOFC anode tubes coated with cuprous oxide;
s13, placing the obtained SOFC anode tube subjected to the hydrothermal treatment into a muffle furnace, heating to 700 ℃, preserving heat for 1 hour, and performing high-temperature oxidation to obtain an SOFC anode tube coated by copper oxide;
s14, placing the product obtained in the step S13 into a vacuum tube furnace, exhausting air, introducing hydrogen at the flow rate of 20sccm, heating the furnace to 800 ℃ in the atmosphere, keeping the temperature for 4 hours, and cooling to room temperature to obtain the SOFC anode coated with copper particles, namely the copper-nickel bimetallic catalyst taking the SOFC anode as a carrier.
Example 2:
the preparation method of the copper-nickel bimetallic catalyst with the micro-triangular tube type SOFC anode as the carrier comprises the following steps:
s11, taking 50 parts of anhydrous copper sulfate solution, carrying out constant-temperature water bath, putting into an SOFC anode tube, sequentially adding 11 parts of formaldehyde solution and ammonia water by mass, adjusting the pH value to 5.4, and carrying out constant-temperature water bath reaction for 40 minutes under the magnetic stirring of 460RPM to obtain a mixed solution and a precursor required by a hydrothermal method;
s12, pouring the obtained SOFC anode tube, the hydrothermal precursor and the mixed solution into a customized hydrothermal kettle, putting the kettle into a drying box, heating to 200 ℃ for reaction for 8 hours, and then cooling to room temperature to obtain a hydrothermal product: SOFC anode triangular tubes coated by cuprous oxide;
s13, placing the obtained SOFC anode tube subjected to the hydrothermal treatment into a muffle furnace, heating to 700 ℃, preserving heat for 1 hour, and performing high-temperature oxidation to obtain an SOFC anode tube coated by copper oxide;
s14, placing the product obtained in the step S13 into a vacuum tube furnace, exhausting air, introducing hydrogen at the flow rate of 25sccm, heating the furnace to 800 ℃ in the atmosphere, keeping the temperature for 4 hours, and cooling to room temperature to obtain the SOFC anode coated with copper particles, namely the copper-nickel bimetallic catalyst taking the SOFC anode as a carrier.
Example 3:
the invention relates to a special hydrothermal kettle device, which is externally provided with a mechanical transmission stirring device, wherein a stirring head of the stirring device extends into a reaction kettle and can control the stirring speed; the inner container is internally provided with a trepanning for plugging and unplugging the ceramic tube, thereby playing a role in fixing the ceramic tube.
Claims (8)
1. A preparation method of a copper-nickel bimetallic catalyst taking a solid oxide fuel cell SOFC anode as a carrier is characterized by comprising the following steps:
s11, placing the tubular SOFC anode tube in a reaction solution of blue copperas, formaldehyde and ammonia water for constant-temperature water bath to obtain a hydrothermal reaction precursor;
s12, fixing the hydrothermal reaction precursor, the SOFC anode and the residual reaction liquid obtained in the S11 in a hydrothermal kettle, carrying out hydrothermal reaction to obtain copper oxide which grows on the SOFC anode tube and is uniformly distributed and well crystallized, and drying;
s13, placing the SOFC anode tube subjected to water heating in a muffle furnace for calcining and oxidizing to obtain the SOFC anode tube subjected to impurity removal and copper oxide on the SOFC anode tube;
and S14, placing the calcined SOFC anode tube into a tube furnace in a hydrogen atmosphere, and carrying out reduction reaction to reduce NiO in the SOFC anode into Ni so as to obtain the copper-nickel bimetallic catalyst taking the SOFC anode tube as a carrier.
2. The preparation method of claim 1, wherein in S11, 40 to 100ml of 0.5mol/L blue vitriod solution is placed in a constant temperature water bath at 60 ℃, then a tubular SOFC anode material is put in, wherein the tubular SOFC anode material is composed of YSZ and NiO, 3 to 20ml of formaldehyde solution and 5 to 70ml of ammonia water solution are slowly dropped after the constant temperature water bath is carried out for 0.5 to 1 hour, and the water bath is continued for 0.5 to 2 hours, so that the hydrothermal precursor and the SOFC anode tube fully soaked by the solution are obtained.
3. The preparation method according to claim 1, wherein in S12, the hydrothermal reaction precursor, the SOFC anode and the residual reaction liquid obtained in S11 are fixed in a hydrothermal kettle, and then the hydrothermal kettle is put into a drying oven to react for 5-15 hours under the condition of raising the temperature to 150-250 ℃ to obtain the SOFC anode tube after hydrothermal treatment.
4. The method according to claim 1, wherein in S13, the SOFC anode tube after the hydrothermal treatment is placed in a muffle furnace, heated to 400-700 ℃, and kept at the temperature for 0.5-2 hours to obtain the SOFC anode tube after impurity removal and oxidation.
5. The preparation method according to claim 1, wherein in S14, the mass flow meter is adjusted, the flow rate of the mixed gas of hydrogen and argon entering the vacuum tube furnace is controlled to be 10-60 sccm, the tube furnace is arranged to be heated to 550-900 ℃ and then is kept for 2-6 hours, and after the reduction reaction is finished, the SOFC anode tube is taken out to obtain the copper-nickel bimetallic catalyst taking the SOFC anode tube as a carrier.
6. The supported copper-nickel bimetallic catalyst for SOFC anode tubes prepared by the preparation method according to any one of claims 1-5.
7. The hydrothermal kettle device for implementing the preparation method according to any one of claims 1 to 5, wherein a mechanically driven stirring device is arranged outside the hydrothermal kettle, a stirring head of the stirring device extends into the reaction kettle, and the stirring speed is controlled; the inner container is internally provided with a jack for plugging and unplugging an SOFC anode tube, so that the function of fixing the SOFC anode tube is achieved;
the preparation steps of the copper-nickel bimetallic catalyst are as follows:
s11, placing the tubular SOFC anode tube in a reaction solution of blue copperas, formaldehyde and ammonia water for constant-temperature water bath to obtain a hydrothermal reaction precursor;
s12, fixing the hydrothermal reaction precursor, the SOFC anode and the residual reaction liquid obtained in the S11 in a hydrothermal kettle, carrying out hydrothermal reaction to obtain copper oxide which grows on the SOFC anode tube and is uniformly distributed and well crystallized, and drying;
s13, placing the SOFC anode tube subjected to water heating in a muffle furnace for calcining and oxidizing to obtain the SOFC anode tube subjected to impurity removal and copper oxide on the SOFC anode tube;
and S14, placing the calcined SOFC anode tube into a tube furnace in a hydrogen atmosphere, and carrying out reduction reaction to reduce NiO in the SOFC anode into Ni so as to obtain the copper-nickel bimetallic catalyst taking the SOFC anode tube as a carrier.
8. The equipment of claim 7, wherein the inner container of the hydrothermal kettle is made of polytetrafluoroethylene through injection molding, and after the inner container is made, through deep machining, through holes are chiseled on the inner wall, and corners are polished.
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| CN112751044B (en) * | 2020-06-05 | 2022-06-17 | 浙江浙能技术研究院有限公司 | Anode material of solid oxide fuel cell and preparation method thereof |
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| KR101292355B1 (en) * | 2011-10-19 | 2013-08-01 | 한밭대학교 산학협력단 | Fabrication method for porous anode substrate and fabricated porous anode substrate using this method in solid oxide fuel cell |
| KR101345241B1 (en) * | 2012-04-03 | 2013-12-27 | 한밭대학교 산학협력단 | Fabrication methods of porous fuel reforming catalyst based on NiO/YSZ in fuel reforming system and fabricated fuel reforming catalyst |
| CN103007945B (en) * | 2012-12-24 | 2015-06-03 | 南京大学 | Supported copper-nickel alloy nanoparticle catalyst and preparation method of catalyst and application in methane and carbon dioxide reforming synthesis gas |
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