CN107376909A - The preparation method of SOFC is oxygen debt reforming catalyst - Google Patents
The preparation method of SOFC is oxygen debt reforming catalyst Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a kind of preparation method of the oxygen debt reforming catalysts of SOFC, feature is to comprise the following steps：Step 1, it will be fitted into after kaolin, calcined kaolin, talcum, calcination of talc, alumina powder, methylcellulose, carbon dust and polyvinyl alcohol in spherical tank and add water mixing；Step 2：Spherical tank is placed in ball milling in planetary ball mill, then carries out being placed in mud in pug mill after gravity squeezing by mixture in spherical tank and refines, and after then old, extrudes to form cordierite ceramic base substrate by extruder；Step 3：Carrier cordierite ceramic is made in cordierite ceramic base substrate；Step 4：After carrier cordierite ceramic is placed in into nitric acid, it will be put into after carrier cordierite ceramic wash clean in baking oven；Step 5：The carrier cordierite ceramic of step 4 is impregnated into take out after catalyst slurry and dried, is then placed in baking oven, then be calcined；Step 6：The carrier cordierite ceramic of step 5 is impregnated into take out after activating agent and dried, is then toasted, then carries out roasting and forms the oxygen debt reforming catalysts of SOFC.Its advantage is：Improve capacity usage ratio.
Description
Technical field
The present invention relates to a kind of preparation method of the oxygen debt reforming catalysts of SOFC.
Background technology
People have been working hard to find existing compared with high-energy source utilization ratio using energy source side free from environmental pollution again for many years
Formula, and fuel cell is exactly more satisfactory generation technology.Fuel cell has the characteristics that：（1）Energy conversion efficiency is high, it
The chemical energy of fuel is directly converted into electric energy, centre is not limited without combustion process by Carnot cycle.Fuel electricity
Fuel-energy conversion efficiency of cell system is 45%~60%, and the conversion efficiency of thermal power generation and nuclear power is 30%~40%.（2）
Load responding is fast, and running quality is high, and fuel cell can transform to rated power from lowest power in a short time.
At present, on SOFC battery Ni-YSZ, Ni-SDC cermet anodes, it is necessary to the ratio between strict control hydrocarbon and water,
Otherwise preferable fuel catalytic reforming reaction effect is extremely difficult to, and easily produces carbon distribution, carbon distribution can make the active fast of electrode
Speed lowers, and causes the decay of cell output, has a strong impact on the service life of battery.At the same time, anode pole inside reforming
Reaction can cause the serious inequality of Temperature Distribution on electrolyte membrance-electrode " three-in-one " component, in turn result in the stripping of electrode
Or the rupture of " three-in-one " component, SOFC safe and stable operation is threatened.
SOFC battery fuels are mainly methane, propane hydrocarbon fuel gas, and such combustion gas is through that can reform generation H under certain condition2、
CO and CO2, H2And CO occurs electrochemical reaction under the effect of SOFC electrodes and produces electricity, is valuable gases, and CO2It is useless useless
Gas, moderate control O2Supply, effective catalytic action be improve SOFC fuel cell energy utilization rates key.
Involved in the present invention is that fuel is included into CH4、C2H6、C3H8、C4H10Deng hydrocarbon, in oxygen debt supply condition
Under, efficiently reform and produce CO and H2, reduce CO2With C generation.Usual catalytic reforming is to take combustion gas to add vapor to be catalyzed
Reform and produce H2And CO2。
（1）Appropriate oxidation reaction mode
CH4 + 2H2O = CO2+4H2Heat absorption 160KJ/mol
（2）Partial oxidation reaction
CH4 + 1/2O2 = CO + 2H2Release 40 KJ/mol of heat
（3）Complete oxidation
CH4 + 2O2 = CO2 + 2H2O releases 800 KJ/mol of heat
（4）Too low oxidation reaction, carbon is tied by producing
2CO = C + CO2Heat absorption 180KJ/mol
CH4 = C + 2H2Release 80 KJ/mol of heat
As can be seen here：The oxygen supply of appropriateness and efficient catalysis can greatly reform out CO and H2,But hold in the case of oxygen debt
Easy carbon distribution.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art and provides one kind in the case of oxygen debt, can improve part oxygen
Change reaction, avoid producing too low oxidation reaction so as to improve the oxygen debt reforming catalysts of the SOFC of capacity usage ratio.
In order to achieve the above object, the present invention is achieved in that it is the preparation method of the oxygen debt reforming catalysts of SOFC,
It is characterized in that comprise the following steps：
Step 1：By 20wt%~30wt% kaolin, 15wt%~30wt% calcined kaolin, 20wt%~30wt% cunning
Stone, 10wt%~30wt% calcination of talc, 10wt%~20wt% alumina powder, 2wt%~5wt% methylcellulose,
0.5wt%~1.5wt% carbon dust and 0.2wt%~1wt% polyvinyl alcohol form mixture A after being sufficiently mixed, and by mixture A
It is fitted into spherical tank, then adding in spherical tank water makes water and mixture A be mixed to form mixture B, the mass ratio of mixture A and water is
1:1.5；
Step 2：The spherical tank of step 1 is placed in ball milling 2~5 hours in planetary ball mill, then entered the mixture B in spherical tank
Row gravity squeezes, and the moisture filtered out in mixture B forms material moulded pottery not yet put in a kiln to bake, and it is small that material moulded pottery not yet put in a kiln to bake is placed in into mud refining 20~24 in pug mill
When, then after old 34~38 hours, then by extruder extrude to form cordierite ceramic base substrate；
Step 3：The cordierite ceramic base substrate that step 2 obtains is placed in room temperature natural air drying 10~12 hours, is then placed in dry
Dried 8~10 hours at a temperature of 100 DEG C in dry case, then cordierite ceramic base substrate is sintered at a temperature of 1300 DEG C ± 1%
Carrier cordierite ceramic is made within 4~4.5 hours；
Step 4：The carrier cordierite ceramic that step 3 is obtained is placed in dust technology soak 10~30 hours after, with ultrasonic water
By carrier cordierite ceramic wash clean, after the surface impurity for removing carrier cordierite ceramic, carrier cordierite ceramic is put into baking
Dried in case at a temperature of 120 DEG C；The concentration of the dust technology is 2mol/L；
Step 5：Carrier cordierite ceramic Jing Guo step 4 is impregnated into catalyst slurry, dipping 20~30 minutes, then
Control carrier cordierite ceramic is at the uniform velocity left in catalyst slurry with 2~5 cm per minute speed, and after electricity consumption blowing dipping
Carrier cordierite ceramic 1~2 minute, then by the carrier cordierite ceramic naturally dry 10~12 hours, after air-drying
Carrier cordierite ceramic is placed in baking oven, after toasting 2~3 hours at a temperature of 120 DEG C, then again in sintering furnace with 550
DEG C roasting 2~4 hours；Repeat the above steps 2~4 times；
The preparation method of catalyst slurry described in step 5 is：Aluminum nitrate, lanthanum nitrate and zirconium nitrate are thoroughly mixed to form mixed
Compound C, then add and deionized water and mix in mixture C, obtains mixture D, and citric acid and abundant is added in mixture D
Stirring obtains mixture E, and ammoniacal liquor is finally added in mixture E and obtains mixture F, mixture F pH value is 2~4 and mixing
Thing F is in colloidal sol shape；The lanthanum nitrate and aluminum nitrate mass ratio 5wt%~20wt%, zirconium nitrate and aluminum nitrate mass ratio 5wt%~
20wt%, deionized water account for 3wt%~40wt% of mixture C, metal cation molal quantity and citric acid molal quantity in mixture D
Than for 1 ︰ 3；
Step 6：After carrier cordierite ceramic by step 5 is impregnated into activating agent 10~30 minutes, taking-up dries 5~6
Hour, then toasted at a temperature of 120 DEG C 2~3 hours, be calcined 180~200 points at a temperature of 600 DEG C ± 1% again afterwards
It is bell into the oxygen debt reforming catalysts of SOFC；
The preparation method of activating agent described in step 6 is：Chloroplatinic acid, ruthenic chloride and palladium bichloride configuration concentration are 7~10g/L's
The aqueous solution, the mol ratio of the chloroplatinic acid, ruthenic chloride and palladium bichloride is 1:1:1.
The present invention compared with prior art the advantages of be：In the case of oxygen debt, partial oxidation reaction can be improved, avoids producing
Too low oxidation reaction is given birth to so as to improve the oxygen debt reforming catalysts of the SOFC of capacity usage ratio.
Embodiment
The embodiment of the present invention is described further below.Herein it should be noted that for these implementations
The explanation of mode is used to help understand the present invention, but does not form limitation of the invention.In addition, invention described below
As long as involved technical characteristic does not form conflict can and is combined with each other each other in each embodiment.
Embodiment one
It is a kind of preparation method of the oxygen debt reforming catalysts of SOFC, is comprised the following steps：
Step 1：By 20wt% kaolin, 15wt% calcined kaolin, 20wt% talcum, 30wt% calcination of talc,
10wt% alumina powder, 3wt% methylcellulose, 1.5wt% carbon dust and 0.5wt% polyvinyl alcohol are formed after being sufficiently mixed
Mixture A, and mixture A is fitted into spherical tank, then adding water in spherical tank makes water be mixed to form mixture B with mixture A, mixes
The mass ratio of compound A and water is 1:1.5；
Step 2：The spherical tank of step 1 is placed in ball milling 2 hours in planetary ball mill, then carried out the mixture B in spherical tank
Gravity squeezes, and the moisture filtered out in mixture B forms material moulded pottery not yet put in a kiln to bake, material moulded pottery not yet put in a kiln to bake is placed in into mud refining 20 hours in pug mill, so
Afterwards after old 34 hours, then by extruder extrude to form cordierite ceramic base substrate；
Step 3：The cordierite ceramic base substrate that step 2 obtains is placed in room temperature natural air drying 10 hours, is then placed in drying box
Dried 8 hours at a temperature of inherent 100 DEG C, then cordierite ceramic base substrate is sintered 4 hours at a temperature of 1287 DEG C violet is made
Cordierite ceramic carrier；
Step 4：The carrier cordierite ceramic that step 3 is obtained is placed in dust technology soak 10 hours after, with ultrasonic water by violet
Cordierite ceramic carrier wash clean, after the surface impurity for removing carrier cordierite ceramic, carrier cordierite ceramic is put into baking oven
Dried at a temperature of 120 DEG C；The concentration of the dust technology is 2mol/L；
Step 5：Carrier cordierite ceramic Jing Guo step 4 is impregnated into catalyst slurry, impregnates 20 minutes, then controls
Carrier cordierite ceramic is at the uniform velocity left in catalyst slurry with 2 cm per minute speed, and the cordierite after electricity consumption blowing dipping
Ceramic monolith 1 minute, then by the carrier cordierite ceramic naturally dry 10 hours, the carrier cordierite ceramic after air-drying is put
In baking oven, after toasting 2 hours at a temperature of 120 DEG C, then it is calcined 2 hours with 550 DEG C in sintering furnace again；Repeat above-mentioned
Step 2 time；
The preparation method of catalyst slurry described in step 5 is：Aluminum nitrate, lanthanum nitrate and zirconium nitrate are thoroughly mixed to form mixed
Compound C, then add and deionized water and mix in mixture C, obtains mixture D, and citric acid and abundant is added in mixture D
Stirring obtains mixture E, and ammoniacal liquor is finally added in mixture E obtains mixture F, and mixture F pH value is 2 and mixture F
In colloidal sol shape；The lanthanum nitrate accounts for mixing with aluminum nitrate mass ratio 5wt%, zirconium nitrate and aluminum nitrate mass ratio 5wt%, deionized water
Thing C 3wt%, metal cation molal quantity and citric acid mole ratio are 1 ︰ 3 in mixture D；
Step 6：After carrier cordierite ceramic by step 5 is impregnated into activating agent 10 minutes, taking-up is dried 5 hours, is connect
And toast 2 hours at a temperature of 120 DEG C, be calcined at a temperature of 594 DEG C ± 1% that to form SOFC within 180 minutes oxygen debt heavy again afterwards
Whole catalyst；
The preparation method of activating agent described in step 6 is：Chloroplatinic acid, ruthenic chloride and palladium bichloride configuration concentration are the water-soluble of 7g/L
Liquid, the mol ratio of the chloroplatinic acid, ruthenic chloride and palladium bichloride is 1:1:1.
Embodiment two
It is a kind of preparation method of the oxygen debt reforming catalysts of SOFC, is comprised the following steps：
Step 1：By 30wt% kaolin, 16wt% calcined kaolin, 21wt% talcum, 10wt% calcination of talc,
20wt% alumina powder, 2wt% methylcellulose, 0.8wt% carbon dust and 0.2wt% polyvinyl alcohol are formed after being sufficiently mixed
Mixture A, and mixture A is fitted into spherical tank, then adding water in spherical tank makes water be mixed to form mixture B with mixture A, mixes
The mass ratio of compound A and water is 1:1.5；
Step 2：The spherical tank of step 1 is placed in ball milling 3.5 hours in planetary ball mill, then entered the mixture B in spherical tank
Row gravity squeezes, and the moisture filtered out in mixture B forms material moulded pottery not yet put in a kiln to bake, and material moulded pottery not yet put in a kiln to bake is placed in into mud in pug mill refines 22 hours,
Then after old 36 hours, then by extruder extrude to form cordierite ceramic base substrate；
Step 3：The cordierite ceramic base substrate that step 2 obtains is placed in room temperature natural air drying 11 hours, is then placed in drying box
Dried 9 hours at a temperature of inherent 100 DEG C, then cordierite ceramic base substrate is sintered 4.25 hours at a temperature of 1300 DEG C and is made
Carrier cordierite ceramic；
Step 4：The carrier cordierite ceramic that step 3 is obtained is placed in dust technology soak 20 hours after, with ultrasonic water by violet
Cordierite ceramic carrier wash clean, after the surface impurity for removing carrier cordierite ceramic, carrier cordierite ceramic is put into baking oven
Dried at a temperature of 120 DEG C；The concentration of the dust technology is 2mol/L；
Step 5：Carrier cordierite ceramic Jing Guo step 4 is impregnated into catalyst slurry, dipping 20~30 minutes, then
Control carrier cordierite ceramic is at the uniform velocity left in catalyst slurry with 3.5 cm per minute speed, and after electricity consumption blowing dipping
Carrier cordierite ceramic 1.5 minutes, then by the carrier cordierite ceramic naturally dry 11 hours, the cordierite pottery after air-drying
Ceramic carrier is placed in baking oven, then small with 550 DEG C of roastings 3 in sintering furnace again after toasting 2.5 hours at a temperature of 120 DEG C
When；Repeat the above steps 3 times；
The preparation method of catalyst slurry described in step 5 is：Aluminum nitrate, lanthanum nitrate and zirconium nitrate are thoroughly mixed to form mixed
Compound C, then add and deionized water and mix in mixture C, obtains mixture D, and citric acid and abundant is added in mixture D
Stirring obtains mixture E, and ammoniacal liquor is finally added in mixture E obtains mixture F, and mixture F pH value is 3 and mixture F
In colloidal sol shape；The lanthanum nitrate and aluminum nitrate mass ratio 12.5wt%, zirconium nitrate and aluminum nitrate mass ratio 12.5wt%, deionized water
Account for the 21.5wt% of mixture C, metal cation molal quantity and citric acid mole ratio are 1 ︰ 3 in mixture D；
Step 6：After carrier cordierite ceramic by step 5 is impregnated into activating agent 20 minutes, taking-up is dried 5.5 hours,
Then toast 2.5 hours at a temperature of 120 DEG C, be calcined at a temperature of 600 DEG C that to form SOFC within 190 minutes oxygen debt heavy again afterwards
Whole catalyst；
The preparation method of activating agent described in step 6 is：Chloroplatinic acid, ruthenic chloride and palladium bichloride configuration concentration are 8.5g/L water
Solution, the mol ratio of the chloroplatinic acid, ruthenic chloride and palladium bichloride is 1:1:1.
Embodiment three
It is a kind of preparation method of the oxygen debt reforming catalysts of SOFC, is comprised the following steps：
Step 1：By 21.5wt% kaolin, 15wt% calcined kaolin, 30wt% talcum, 15wt% calcination of talc,
12wt% alumina powder, 5wt% methylcellulose, 0.5wt% carbon dust and 1wt% polyvinyl alcohol form mixed after being sufficiently mixed
Compound A, and mixture A is fitted into spherical tank, then adding water in spherical tank makes water be mixed to form mixture B with mixture A, mixes
The mass ratio of thing A and water is 1:1.5；
Step 2：The spherical tank of step 1 is placed in ball milling 5 hours in planetary ball mill, then carried out the mixture B in spherical tank
Gravity squeezes, and the moisture filtered out in mixture B forms material moulded pottery not yet put in a kiln to bake, material moulded pottery not yet put in a kiln to bake is placed in into mud refining 24 hours in pug mill, so
Afterwards after old 38 hours, then by extruder extrude to form cordierite ceramic base substrate；
Step 3：The cordierite ceramic base substrate that step 2 obtains is placed in room temperature natural air drying 12 hours, is then placed in drying box
Dried 10 hours at a temperature of inherent 100 DEG C, then cordierite ceramic base substrate is sintered 4.5 hours at a temperature of 1313 DEG C and is made
Carrier cordierite ceramic；
Step 4：The carrier cordierite ceramic that step 3 is obtained is placed in dust technology soak 30 hours after, with ultrasonic water by violet
Cordierite ceramic carrier wash clean, after the surface impurity for removing carrier cordierite ceramic, carrier cordierite ceramic is put into baking oven
Dried at a temperature of 120 DEG C；The concentration of the dust technology is 2mol/L；
Step 5：Carrier cordierite ceramic Jing Guo step 4 is impregnated into catalyst slurry, impregnates 30 minutes, then controls
Carrier cordierite ceramic is at the uniform velocity left in catalyst slurry with 5 cm per minute speed, and the cordierite after electricity consumption blowing dipping
Ceramic monolith 2 minutes, then by the carrier cordierite ceramic naturally dry 12 hours, the carrier cordierite ceramic after air-drying is put
In baking oven, after toasting 3 hours at a temperature of 120 DEG C, then it is calcined 4 hours with 550 DEG C in sintering furnace again；Repeat above-mentioned
Step 4 time；
The preparation method of catalyst slurry described in step 5 is：Aluminum nitrate, lanthanum nitrate and zirconium nitrate are thoroughly mixed to form mixed
Compound C, then add and deionized water and mix in mixture C, obtains mixture D, and citric acid and abundant is added in mixture D
Stirring obtains mixture E, and ammoniacal liquor is finally added in mixture E obtains mixture F, and mixture F pH value is 4 and mixture F
In colloidal sol shape；The lanthanum nitrate and aluminum nitrate mass ratio 20wt%, zirconium nitrate and aluminum nitrate mass ratio 20wt%, deionized water accounts for mixed
Compound C 40wt%, metal cation molal quantity and citric acid mole ratio are 1 ︰ 3 in mixture D；
Step 6：After carrier cordierite ceramic by step 5 is impregnated into activating agent 30 minutes, taking-up is dried 6 hours, is connect
And toasted at a temperature of 120 DEG C 3 hours, be calcined the oxygen debt reformations of formation SOFC in 200 minutes at a temperature of 606 DEG C again afterwards and urge
Agent；
The preparation method of activating agent described in step 6 is：Chloroplatinic acid, ruthenic chloride and palladium bichloride configuration concentration are the water-soluble of 10g/L
Liquid, the mol ratio of the chloroplatinic acid, ruthenic chloride and palladium bichloride is 1:1:1.
Example IV
It is a kind of preparation method of the oxygen debt reforming catalysts of SOFC, is comprised the following steps：
Step 1：By 20wt% kaolin, 30wt% calcined kaolin, 20wt% talcum, 10wt% calcination of talc,
13wt% alumina powder, 5wt% methylcellulose, 1wt% carbon dust and 1wt% polyvinyl alcohol form mixing after being sufficiently mixed
Thing A, and mixture A is fitted into spherical tank, then adding water in spherical tank makes water be mixed to form mixture B, mixture with mixture A
The mass ratio of A and water is 1:1.5；
Step 2：The spherical tank of step 1 is placed in ball milling 3 hours in planetary ball mill, then carried out the mixture B in spherical tank
Gravity squeezes, and the moisture filtered out in mixture B forms material moulded pottery not yet put in a kiln to bake, material moulded pottery not yet put in a kiln to bake is placed in into mud refining 21 hours in pug mill, so
Afterwards after old 35 hours, then by extruder extrude to form cordierite ceramic base substrate；
Step 3：The cordierite ceramic base substrate that step 2 obtains is placed in room temperature natural air drying 11 hours, is then placed in drying box
Dried 9 hours at a temperature of inherent 100 DEG C, then cordierite ceramic base substrate is sintered 4.5 hours at a temperature of 1300 DEG C and is made
Carrier cordierite ceramic；
Step 4：The carrier cordierite ceramic that step 3 is obtained is placed in dust technology soak 30 hours after, with ultrasonic water by violet
Cordierite ceramic carrier wash clean, after the surface impurity for removing carrier cordierite ceramic, carrier cordierite ceramic is put into baking oven
Dried at a temperature of 120 DEG C；The concentration of the dust technology is 2mol/L；
Step 5：Carrier cordierite ceramic Jing Guo step 4 is impregnated into catalyst slurry, impregnates 20 minutes, then controls
Carrier cordierite ceramic is at the uniform velocity left in catalyst slurry with 5 cm per minute speed, and the cordierite after electricity consumption blowing dipping
Ceramic monolith 1 minute, then by the carrier cordierite ceramic naturally dry 12 hours, the carrier cordierite ceramic after air-drying is put
In baking oven, after toasting 3 hours at a temperature of 120 DEG C, then it is calcined 2 hours with 550 DEG C in sintering furnace again；Repeat above-mentioned
Step 2 time；
The preparation method of catalyst slurry described in step 5 is：Aluminum nitrate, lanthanum nitrate and zirconium nitrate are thoroughly mixed to form mixed
Compound C, then add and deionized water and mix in mixture C, obtains mixture D, and citric acid and abundant is added in mixture D
Stirring obtains mixture E, and ammoniacal liquor is finally added in mixture E obtains mixture F, and mixture F pH value is 3 and mixture F
In colloidal sol shape；The lanthanum nitrate and aluminum nitrate mass ratio 10wt%, zirconium nitrate and aluminum nitrate mass ratio 12wt%, deionized water accounts for mixed
Compound C 30wt%, metal cation molal quantity and citric acid mole ratio are 1 ︰ 3 in mixture D；
Step 6：After carrier cordierite ceramic by step 5 is impregnated into activating agent 13 minutes, taking-up is dried 6 hours, is connect
And toasted at a temperature of 120 DEG C 2 hours, be calcined the oxygen debt reformations of formation SOFC in 180 minutes at a temperature of 600 DEG C again afterwards and urge
Agent；
The preparation method of activating agent described in step 6 is：Chloroplatinic acid, ruthenic chloride and palladium bichloride configuration concentration are 7.9g/L water
Solution, the mol ratio of the chloroplatinic acid, ruthenic chloride and palladium bichloride is 1:1:1.
Embodiments of the present invention are explained in detail above, but the present invention is not limited to described embodiment.
For the ordinary skill in the art, in the case where not departing from the principle and objective of the present invention to these embodiments
A variety of changes, modification, replacement and deformation is carried out to still fall within the scope of the present invention.
Claims (1)
1. a kind of preparation method of the oxygen debt reforming catalysts of SOFC, it is characterised in that comprise the following steps：
Step 1：By 20wt%~30wt% kaolin, 15wt%~30wt% calcined kaolin, 20wt%~30wt% cunning
Stone, 10wt%~30wt% calcination of talc, 10wt%~20wt% alumina powder, 2wt%~5wt% methylcellulose,
0.5wt%~1.5wt% carbon dust and 0.2wt%~1wt% polyvinyl alcohol form mixture A after being sufficiently mixed, and mixture A is filled
Enter in spherical tank, then adding in spherical tank water makes water and mixture A be mixed to form mixture B, the mass ratio of mixture A and water is 1:
1.5；
Step 2：The spherical tank of step 1 is placed in ball milling 2~5 hours in planetary ball mill, then entered the mixture B in spherical tank
Row gravity squeezes, and the moisture filtered out in mixture B forms material moulded pottery not yet put in a kiln to bake, and it is small that material moulded pottery not yet put in a kiln to bake is placed in into mud refining 20~24 in pug mill
When, then after old 34~38 hours, then by extruder extrude to form cordierite ceramic base substrate；
Step 3：The cordierite ceramic base substrate that step 2 obtains is placed in room temperature natural air drying 10~12 hours, is then placed in dry
Dried 8~10 hours at a temperature of 100 DEG C in dry case, then cordierite ceramic base substrate is sintered at a temperature of 1300 DEG C ± 1%
Carrier cordierite ceramic is made within 4~4.5 hours；
Step 4：The carrier cordierite ceramic that step 3 is obtained is placed in dust technology soak 10~30 hours after, with ultrasonic water
By carrier cordierite ceramic wash clean, after the surface impurity for removing carrier cordierite ceramic, carrier cordierite ceramic is put into baking
Dried in case at a temperature of 120 DEG C；The concentration of the dust technology is 2mol/L；
Step 5：Carrier cordierite ceramic Jing Guo step 4 is impregnated into catalyst slurry, dipping 20~30 minutes, then
Control carrier cordierite ceramic is at the uniform velocity left in catalyst slurry with 2~5 cm per minute speed, and after electricity consumption blowing dipping
Carrier cordierite ceramic 1~2 minute, then by the carrier cordierite ceramic naturally dry 10~12 hours, after air-drying
Carrier cordierite ceramic is placed in baking oven, after toasting 2~3 hours at a temperature of 120 DEG C, then again in sintering furnace with 550
DEG C roasting 2~4 hours；Repeat the above steps 2~4 times；
The preparation method of catalyst slurry described in step 5 is：Aluminum nitrate, lanthanum nitrate and zirconium nitrate are thoroughly mixed to form mixed
Compound C, then add and deionized water and mix in mixture C, obtains mixture D, and citric acid and abundant is added in mixture D
Stirring obtains mixture E, and ammoniacal liquor is finally added in mixture E and obtains mixture F, mixture F pH value is 2~4 and mixing
Thing F is in colloidal sol shape；The lanthanum nitrate and aluminum nitrate mass ratio 5wt%~20wt%, zirconium nitrate and aluminum nitrate mass ratio 5wt%~
20wt%, deionized water account for 3wt%~40wt% of mixture C, metal cation molal quantity and citric acid molal quantity in mixture D
Than for 1 ︰ 3；
Step 6：After carrier cordierite ceramic by step 5 is impregnated into activating agent 10~30 minutes, taking-up dries 5~6
Hour, then toasted at a temperature of 120 DEG C 2~3 hours, be calcined 180~200 points at a temperature of 600 DEG C ± 1% again afterwards
It is bell into the oxygen debt reforming catalysts of SOFC；
The preparation method of activating agent described in step 6 is：Chloroplatinic acid, ruthenic chloride and palladium bichloride configuration concentration are 7~10g/L's
The aqueous solution, the mol ratio of the chloroplatinic acid, ruthenic chloride and palladium bichloride is 1:1:1.
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| CN106797044A (en) * | 2014-10-07 | 2017-05-31 | 布罗托尼克斯技术公司 | SOFC conducts |
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- 2017-06-12 CN CN201710436009.0A patent/CN107376909A/en active Pending
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| CN1921937A (en) * | 2004-02-19 | 2007-02-28 | 出光兴产株式会社 | Reforming catalyst for hydrocarbon, method for producing hydrogen using the same, and fuel cell system |
| CN101385973A (en) * | 2008-11-05 | 2009-03-18 | 中国海洋石油总公司 | Preparation method of cleaning catalyst capable of increasing low-temperature initiation performance |
| CN103460476A (en) * | 2011-04-01 | 2013-12-18 | Toto株式会社 | Method for producing cerium complex oxide, solid oxide fuel cell, and fuel cell system |
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