CN106848336A - A kind of preparation method and its equipment with SOFC plate-load cuprum nickle duplex metal catalyst - Google Patents
A kind of preparation method and its equipment with SOFC plate-load cuprum nickle duplex metal catalyst Download PDFInfo
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- CN106848336A CN106848336A CN201611175461.8A CN201611175461A CN106848336A CN 106848336 A CN106848336 A CN 106848336A CN 201611175461 A CN201611175461 A CN 201611175461A CN 106848336 A CN106848336 A CN 106848336A
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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
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Abstract
The preparation method and its equipment of the cuprum nickle duplex metal catalyst the present invention relates to one kind with SOFC (SOFC) anode as carrier, including obtaining hydro-thermal reaction predecessor, the hydro-thermal reaction predecessor of gained, SOFC anodes and solution are fixed in especially customized water heating kettle, carry out hydro-thermal reaction, obtain being grown in being evenly distributed in SOFC anode tubes, the oxide of the copper of complete crystallization, then be dried；The SOFC anode tubes that hydro-thermal is crossed are placed in calcined oxide in Muffle furnace, obtain the SOFC anode tubes after the removal of impurity and the upper Cu oxide of pipe；SOFC anode tubes after calcining are put into the tube furnace of atmosphere of hydrogen, reduction reaction is carried out, the NiO in SOFC anodes is also reduced into Ni, it is possible to obtain the cuprum nickle duplex metal catalyst with SOFC anodes as carrier.The equipment is special water heating kettle.
Description
Technical field：
The invention belongs to application chemical industry, energy field, it is related to SOFC (SOFC) plate-load copper, nickel
Bimetallic catalyst preparation method.
Background technology：
In recent years, bimetallic catalyst is very active in catalyticing research, and research shows：The activity of bimetallic catalyst is high
In corresponding single component catalyst, and catalyst choice difference is also very big.And YSZ supported coppers, the double gold of nickel that the present invention is used
Metal catalyst can use catalyst as hydrogen production from methanol-steam reforming (MSR).
SOFC (SOFC) is a kind of energy that the chemical energy of hydrocarbon fuel is converted into electric energy
Reforming unit, can also have the function that fuel gas is reformed, by hydrocarbon combustion by SOFC anodes by appropriate design improvement
Material is allowed to be converted into the hydrogen and carbon monoxide of small molecule by appropriate passivation and reformation, and it is anti-to be just smoothed out electrochemistry
Should, produce electric energy.
The conventional preparation method of catalyst has infusion process, the precipitation method, thermal solution retorting process, hydro-thermal method etc..Processed by hydro-thermal method,
The powder of complete crystallization, preferable crystallite dimension can be obtained；And hydro-thermal method preparation technology is fairly simple by contrast, and with
SOFC anodes are made to generate copper on carrier as carrier with hydro-thermal method, can reach and even copper particle is formed on carrier
Purpose, strengthens its catalytic effect.
Compared with traditional hydrogen production process, preparing hydrogen by reforming methanol has following 3 advantages：
(1) hydrogen feedstock wide material sources and cheap, methyl alcohol, both can be from fossil used as a kind of common industrial chemicals
It is obtained in resource, can be obtained from biomass again；
(2) protium utilization rate is high, and methanol molecules formula is CH3OH, hydrogen content is high, and energy density is high, and the yield of hydrogen is high；
(3) device for producing hydrogen is simple, and methyl alcohol is easy to store and is transported, and can make assembly type or packaged type hydrogen from methyl alcohol dress
Put.
The content of the invention：
The present invention is to prepare a kind of cuprum nickle duplex metal with SOFC (SOFC) anode as carrier
Catalyst, is mainly used in the reformation of hydrocarbon fuel, can be as the internal reformer of SOFC TRTs or external reformer.
To achieve the above object, a kind of double gold of cupro-nickel with SOFC (SOFC) anode as carrier are prepared
Metal catalyst, the technical solution adopted by the present invention is divided into following steps：
S11, take tubular SOFC anode tube and be placed in water bath with thermostatic control in the reaction solution of cupric sulfate pentahydrate, formaldehyde, ammoniacal liquor, obtain water
Thermal response predecessor；
S12, the hydro-thermal reaction predecessor of gained, SOFC anodes and solution in S11 are fixed on especially customized water heating kettle
In, hydro-thermal reaction is carried out, obtain being grown in being evenly distributed in SOFC anode tubes, the oxide of the copper of complete crystallization, then carry out
Dry；
S13, the SOFC anode tubes for crossing hydro-thermal are placed in calcined oxide in Muffle furnace, obtain the SOFC anodes after the removal of impurity
Pipe and the upper Cu oxide of pipe；
S14, the SOFC anode tubes after calcining are put into the tube furnace of atmosphere of hydrogen, carry out reduction reaction, SOFC sun
NiO in extremely is also reduced into Ni, it is possible to obtain the cuprum nickle duplex metal catalyst with SOFC anodes as carrier.
Further, in S11, first by the concentration of 40~100ml for the cupric sulfate pentahydrate solution of 0.5mol/L is placed in 60
Among DEG C water bath with thermostatic control, then tubular SOFC anode material (being made up of YSZ and NiO) is put into, after water bath with thermostatic control 0.5-1 hours, then
Be slowly added dropwise 3~20ml formalins and 5~70ml ammonia spirits, continue water-bath 0.5~2 hour, obtain hydro-thermal predecessor and
The SOFC anode tubes fully soaked by solution.
Further, in S12, S11 gained liquid, predecessor, SOFC anodes are placed among water heating kettle.Place into dry
Dry case, reacts 5~15 hours under the conditions of being warming up to 150~250 DEG C, obtains the SOFC anode tubes after hydro-thermal process.
Further, above-mentioned water heating kettle is for the present inventor designs alone and looks for specialized factory's delicate execution, the water heating kettle
Inner bag polytetrafluoroethylene (PTFE) by special processing, one is wall of inner container has the jack of many places 2mm or so, can be used to stablize fixation
Firmly SOFC anode tubes, it is therefore an objective under agitation, stabilized porous ceramic pipe；The second is there have superfine stainless pin to penetrate to be slotting
In hole, and through wall of inner container, using this root conductor, pulse voltage can be applied to the liquid in water heating kettle, it is therefore an objective to utilize arteries and veins
The electrostatic attraction of voltage generation is rushed, increases the fluctuation of energy in the region, copper ion is gathered in around SOFC anode tubes, make jack
The nucleus generation in region is more, thirdly mechanically operated agitating device is arranged at water heating kettle top, its stirring vane is directly inserted
Enter to below reaction liquid level, can reach carries out hydro-thermal reaction under agitation.
In such scheme, polytetrafluoroethylliner liner is formed by mold injection, good with excellent corrosion resistance
Self lubricity and adhesion.After inner bag is obtained, then by mechanical deep processing, chisel through hole, corner polishing are carried out in inwall.
In such scheme, pulse voltage is interval discrete pulse.
Further, in S13, the SOFC anode tubes after above-mentioned hydro-thermal process are put into Muffle furnace, is warmed up to 400
~700 DEG C, 0.5~2 hour is incubated, obtains the SOFC anode tubes after the removal of impurity, oxidation.
Further, in S14, mass flowmenter is adjusted, control enters the hydrogen and argon gas gaseous mixture of vacuum tube furnace
Flow between 10~60sccm, set tube furnace be warming up to 550~900 DEG C under the conditions of be incubated 2~6 hours, reduction reaction
After end, SOFC anode tubes are taken out, obtain the cuprum nickle duplex metal catalyst with SOFC anodes as carrier.
Brief description of the drawings：
Fig. 1 is the product structure figure of special water heating kettle；
Fig. 2 is the SEM pictures by the cupro-nickel composite catalyst obtained after S13 steps；
Fig. 3 is the SEM pictures by the cupro-nickel composite catalyst obtained after S14 steps.
Specific embodiment：
Embodiment 1：
The preparation method of the cuprum nickle duplex metal catalyst with micro- circular pipe type SOFC anodes as carrier, comprises the following steps：
S11, mass fraction is taken for 50 parts of cupric sulfate pentahydrate solution carry out water bath with thermostatic control, then put into SOFC anode tubes, then
Sequentially add formalin and ammoniacal liquor that mass fraction is 7 parts, regulation pH value to 3.6, the constant temperature under the magnetic agitation of 400RPM
Water-bath 30 minutes, mixed solution and predecessor needed for obtaining hydro-thermal method；
S12, SOFC anode tubes obtained above, hydro-thermal predecessor and mixed solution are poured into customized water heating kettle, then put
Enter drying box, be warming up to 240 DEG C of 8 hours of reaction, room temperature is cooled to afterwards, obtain its hydrothermal product：It is oxidized cuprous cladding
SOFC anode tubes；
The SOFC anode tubes that S13, the hydro-thermal process that will be obtained are crossed are placed into Muffle furnace, are warming up to 700 DEG C of insulations 1 small
When, through high-temperature oxydation after, obtain be oxidized copper clad SOFC anode tubes；
S14, the product that will be obtained in S13 again are put into vacuum tube furnace, logical with the flow of 20sccm after extracting air
Enter hydrogen, under this atmosphere, stove is warmed up to 800 DEG C of 4 hours of insulation, after being cooled to room temperature afterwards, obtain by copper particle bag
The SOFC anodes for covering, i.e., the cuprum nickle duplex metal catalyst with SOFC anodes as carrier.
Embodiment 2：
The preparation method of the cuprum nickle duplex metal catalyst with micro- triangle tubular type SOFC anodes as carrier, comprises the following steps：
S11, the anhydrous slufuric acid copper solution for taking 50 parts carry out water bath with thermostatic control, then put into SOFC anode tubes, sequentially add matter
Amount number is 11 parts of formalin and ammoniacal liquor, and to 5.4, water bath with thermostatic control reacts 40 to regulation pH value under the magnetic agitation of 460RPM
Minute, mixed solution and predecessor needed for obtaining hydro-thermal method；
S12, SOFC anode tubes obtained above, hydro-thermal predecessor and mixed solution are poured into customized water heating kettle, then put
Enter drying box, be warming up to 200 DEG C of 8 hours of reaction, room temperature is cooled to afterwards, obtain its hydrothermal product：It is oxidized cuprous cladding
SOFC anode triangular pipes；
The SOFC anode tubes that S13, the hydro-thermal process that will be obtained are crossed are placed into Muffle furnace, are warming up to 700 DEG C and are incubated 1
Hour, through high-temperature oxydation after, obtain be oxidized copper clad SOFC anode tubes；
S14, the product that will be obtained in S13 again are put into vacuum tube furnace, logical with the flow of 25sccm after extracting air
Enter hydrogen, under this atmosphere, stove is warmed up to 800 DEG C of 4 hours of insulation, after being cooled to room temperature afterwards, obtain by copper particle bag
The SOFC anodes for covering, i.e., the cuprum nickle duplex metal catalyst with SOFC anodes as carrier.
Embodiment 3：
There is mechanically operated agitating device the special water heating kettle equipment that the present invention relates to, outside, and its stirring-head is stretched
Enter inside reactor, and stir speed (S.S.) can be controlled；Having inside inner bag can play fixed pottery for the set hole of earthenware plug
The effect of porcelain tube.
Claims (8)
1. the preparation method of cuprum nickle duplex metal catalyst of the one kind with SOFC (SOFC) anode as carrier, its
It is characterised by, comprises the following steps：
S11, take tubular SOFC anode tube and be placed in water bath with thermostatic control in the reaction solution of cupric sulfate pentahydrate, formaldehyde, ammoniacal liquor, obtain hydro-thermal anti-
Answer predecessor；
S12, the hydro-thermal reaction predecessor of gained, SOFC anodes and solution in S11 are fixed in especially customized water heating kettle, entered
Water-filling thermal response, obtains being grown in being evenly distributed in SOFC anode tubes, the oxide of the copper of complete crystallization, then be dried；
S13, the SOFC anode tubes for crossing hydro-thermal are placed in calcined oxide in Muffle furnace, obtain the SOFC anode tubes after the removal of impurity and
Cu oxide on pipe；
S14, the SOFC anode tubes after calcining are put into the tube furnace of atmosphere of hydrogen, reduction reaction are carried out, in SOFC anodes
NiO be also reduced into Ni, it is possible to obtain the cuprum nickle duplex metal catalyst with SOFC anodes as carrier.
2. preparation method as claimed in claim 1, it is characterised in that in S11, be by the concentration of 40~100ml first
The cupric sulfate pentahydrate solution of 0.5mol/L is placed among 60 DEG C of waters bath with thermostatic control, then put into tubular SOFC anode material (by YSZ and
NiO is constituted), after water bath with thermostatic control 0.5-1 hours, then 3~20ml formalins and 5~70ml ammonia spirits are slowly added dropwise, continue
Water-bath 0.5~2 hour, obtains hydro-thermal predecessor and the SOFC anode tubes fully soaked by solution.
3. preparation method as claimed in claim 1, it is characterised in that in S12, by S11 gained liquid, predecessor, SOFC
Anode is placed among water heating kettle.Drying box is placed into, is reacted 5~15 hours under the conditions of being warming up to 150~250 DEG C, obtain hydro-thermal
SOFC anode tubes after treatment.
4. preparation method as claimed in claim 1, it is characterised in that in S13, by the SOFC anodes after above-mentioned hydro-thermal process
Pipe is put into Muffle furnace, is warmed up to 400~700 DEG C, is incubated 0.5~2 hour, obtains the SOFC sun after the removal of impurity, oxidation
Pole pipe.
5. preparation method as claimed in claim 1, it is characterised in that in S14, adjusts mass flowmenter, and control enters true
The hydrogen of empty tube furnace and the flow of argon gas gaseous mixture set tube furnace and are warming up to 550~900 DEG C of bars between 10~60sccm
2~6 hours are incubated under part, after reduction reaction terminates, SOFC anode tubes is taken out, the double gold of cupro-nickel with SOFC anodes as carrier are obtained
Metal catalyst.
6. the cuprum nickle duplex metal with SOFC anodes as carrier that the preparation method as described in claim any one of 1-5 is prepared
Catalyst.
7. the water heating kettle equipment of the preparation method as described in any one as described in claim 1-5 is implemented, it is characterised in that hydro-thermal
There is mechanically operated agitating device outside kettle, its stirring-head is stretched into inside reactor, and stir speed (S.S.) can be controlled；In inner bag
Portion has can play a part of fixed earthenware for the jack of earthenware plug.
8. equipment according to claim 7, it is characterised in that the inner bag polytetrafluoroethylene (PTFE) of the water heating kettle by special plus
Work.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611175461.8A CN106848336B (en) | 2016-12-19 | 2016-12-19 | Preparation method and equipment of SOFC anode loaded copper-nickel bimetallic catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611175461.8A CN106848336B (en) | 2016-12-19 | 2016-12-19 | Preparation method and equipment of SOFC anode loaded copper-nickel bimetallic catalyst |
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| CN106848336A true CN106848336A (en) | 2017-06-13 |
| CN106848336B CN106848336B (en) | 2020-04-17 |
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| CN201611175461.8A Expired - Fee Related CN106848336B (en) | 2016-12-19 | 2016-12-19 | Preparation method and equipment of SOFC anode loaded copper-nickel bimetallic catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110619792A (en) * | 2019-09-23 | 2019-12-27 | 佛山索弗克氢能源有限公司 | Portable fuel cell teaching instrument |
| CN112751044A (en) * | 2020-06-05 | 2021-05-04 | 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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| CN101862658A (en) * | 2010-06-28 | 2010-10-20 | 济南大学 | ZrO2 loaded copper and nickel catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110619792A (en) * | 2019-09-23 | 2019-12-27 | 佛山索弗克氢能源有限公司 | Portable fuel cell teaching instrument |
| CN112751044A (en) * | 2020-06-05 | 2021-05-04 | 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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