CN107376909A - The preparation method of SOFC is oxygen debt reforming catalyst - Google Patents

The preparation method of SOFC is oxygen debt reforming catalyst Download PDF

Info

Publication number
CN107376909A
CN107376909A CN201710436009.0A CN201710436009A CN107376909A CN 107376909 A CN107376909 A CN 107376909A CN 201710436009 A CN201710436009 A CN 201710436009A CN 107376909 A CN107376909 A CN 107376909A
Authority
CN
China
Prior art keywords
cordierite ceramic
mixture
hours
carrier
carrier cordierite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710436009.0A
Other languages
Chinese (zh)
Inventor
杨华政
梁波
吴钢
李斯琳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Foshan Suofuke Hydrogen Energy Co Ltd
Original Assignee
Foshan Suofuke Hydrogen Energy Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Foshan Suofuke Hydrogen Energy Co Ltd filed Critical Foshan Suofuke Hydrogen Energy Co Ltd
Priority to CN201710436009.0A priority Critical patent/CN107376909A/en
Publication of CN107376909A publication Critical patent/CN107376909A/en
Pending legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54Catalysts 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
    • B01J23/56Platinum group metals
    • B01J23/63Platinum group metals with rare earths or actinides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/009Preparation by separation, e.g. by filtration, decantation, screening
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/024Multiple impregnation or coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • C01B3/38Production 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
    • C01B3/40Production 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06Integration with other chemical processes
    • C01B2203/066Integration with other chemical processes with fuel cells
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041Composition of the catalyst
    • C01B2203/1047Group VIII metal catalysts
    • C01B2203/1064Platinum group metal catalysts
    • C01B2203/107Platinum catalysts
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205Composition of the feed
    • C01B2203/1211Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235Hydrocarbons
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

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

The preparation method of SOFC is oxygen debt reforming catalyst
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.
CN201710436009.0A 2017-06-12 2017-06-12 The preparation method of SOFC is oxygen debt reforming catalyst Pending CN107376909A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710436009.0A CN107376909A (en) 2017-06-12 2017-06-12 The preparation method of SOFC is oxygen debt reforming catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710436009.0A CN107376909A (en) 2017-06-12 2017-06-12 The preparation method of SOFC is oxygen debt reforming catalyst

Publications (1)

Publication Number Publication Date
CN107376909A true CN107376909A (en) 2017-11-24

Family

ID=60332393

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710436009.0A Pending CN107376909A (en) 2017-06-12 2017-06-12 The preparation method of SOFC is oxygen debt reforming catalyst

Country Status (1)

Country Link
CN (1) CN107376909A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106797044A (en) * 2014-10-07 2017-05-31 布罗托尼克斯技术公司 SOFC conducts

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106797044A (en) * 2014-10-07 2017-05-31 布罗托尼克斯技术公司 SOFC conducts

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
林彬荫等: "《耐火材料原料》", 30 November 2015, 冶金工业出版社 *

Similar Documents

Publication Publication Date Title
CN105529472B (en) Flake porous two-dimentional carbon material of a kind of Co-N codope and preparation method thereof
CN104399508B (en) Nitrogen-sulfur co-doped carbon material with electro-catalytic oxygen reduction activity and preparation method of carbon material
CN105107536A (en) Preparation method of polyhedral cobalt phosphide catalyst for hydrogen production through water electrolysis
CN104971760B (en) The preparation method of sulfur-bearing, nitrogen and transition metal macropore carbon oxygen reduction catalyst
CN111146456B (en) Preparation method of composite cathode material for fuel cell
CN113745540B (en) Anode reforming layer of direct alcohol fuel cell and preparation method and application thereof
CN105056961B (en) Perovskite composite catalyst that amorphous non-noble metal hydroxide for oxygen evolution reaction is modified and preparation method thereof
CN102867965A (en) Porous microsphere perovskite type calcium manganese oxide compound and preparation method and application thereof
CN103746134A (en) Electrolyte for solid oxide fuel cell and preparation method thereof
CN109898093A (en) A kind of 3D structure composite hydrogen-precipitating electrode and preparation method thereof
CN115241471B (en) Cathode material of solid oxide fuel cell and preparation method and application thereof
CN102824918B (en) Graphene oxide rare-earth composite methane catalyst
CN111244470A (en) Nano composite cathode and preparation and application thereof
CN106602087A (en) Nickel-cobalt-manganese-carbon nanotube difunctional composite catalyst and preparation method and application thereof
CN110655120B (en) Preparation method of mesoporous spherical nickel cobaltate nano material
US8877118B2 (en) Methods of producing anodes for solid oxide fuel cells
CN105576258A (en) Preparation method of Ir0.08Ti0.92O2 nano-powder catalyst
CN104328456B (en) Reversible phase transition vanadate electrode material, and preparation method and application thereof
WO2024066179A1 (en) Surface-modified perovskite oxide electrocatalyst as well as preparation method therefor and use thereof
CN113979475A (en) Preparation method and application of chromium lithium titanate negative electrode material
CN108539160A (en) CoO/rGO compound and preparation method and application thereof
CN116082028B (en) Proton ceramic fuel cell anode material, preparation method and application thereof in direct ammonia fuel cell
CN107376909A (en) The preparation method of SOFC is oxygen debt reforming catalyst
CN101607199B (en) CO selective methanation monolithic catalyst and preparation method thereof
CN110534758A (en) A method of utilizing four three carbon surface modified perovskite oxides of nitridation

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20171124