CN106941185B - SOFC tubular type is oxygen debt, and electrode is reformed in catalysis certainly - Google Patents
SOFC tubular type is oxygen debt, and electrode is reformed in catalysis certainly Download PDFInfo
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- CN106941185B CN106941185B CN201710230965.3A CN201710230965A CN106941185B CN 106941185 B CN106941185 B CN 106941185B CN 201710230965 A CN201710230965 A CN 201710230965A CN 106941185 B CN106941185 B CN 106941185B
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000001301 oxygen Substances 0.000 title claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 17
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 81
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- 238000003411 electrode reaction Methods 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 238000003780 insertion Methods 0.000 claims abstract description 10
- 230000037431 insertion Effects 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 41
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims description 36
- 239000000919 ceramic Substances 0.000 claims description 26
- 239000011230 binding agent Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
- 238000002407 reforming Methods 0.000 claims description 16
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 239000003292 glue Substances 0.000 claims description 9
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 9
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 230000005611 electricity Effects 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 230000004520 agglutination Effects 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- 238000002242 deionisation method Methods 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 14
- 238000010248 power generation Methods 0.000 abstract description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000001294 propane Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000001833 catalytic reforming Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- -1 methane Chemical compound 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
-
- 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
-
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of SOFC tubular type it is oxygen debt catalysis from reform electrode, feature be include confined gas pipe, porous honeycomb catalyst, electrolyte separation layer cathode layer and anode support electrode pipe；Anode support electrode pipe is divided into three sections of workspaces and is followed successively by from left to right from reformation workspace, electrode reaction workspace and vent gas treatment workspace；Porous honeycomb catalyst is embedded in confined gas pipe, and confined gas pipe insertion anode support electrode pipe is reformed in workspace certainly, the length of confined gas pipe and the equal length from reformation workspace；The electrolyte separation layer cathode layer covers on the electrode reaction workspace of anode support electrode pipe, and the length of electrolyte separation layer cathode layer is identical as the length of electrode reaction workspace.It is reformed the fuel into the big critical function cohesion of electrode power generation two in electrode tube, utmostly reduces manufacturing cost, battery weight and the volume of tubular type SOFC fuel cell.
Description
Technical field
The present invention relates to a kind of oxygen debt catalysis of SOFC tubular type from reforming electrode more particularly to a kind of propane (including methane, second
The hydrocarbon gas such as alkane) reforming solid oxide fuel cells tubular pole propane it is whole.
Background technique
SOFC solid oxide fuel cell is by propane (including the hydrocarbon gas such as methane, ethane) in certain temperature
Under the conditions of degree, hydrogen is generated through catalytic reforming, the oxygen in hydrogen and air is raw material, its chemical energy is converted to electric energy.
Usual SOFC is equipped with dedicated reformer apparatus, and overheated steam and propane are passed through reformer by a certain percentage, added
Temperature is to 650 degree, and under nickel-base catalyst effect, propane gas is restructured as H2、CO、CO2。CO2It is useless exhaust gas, it is reformed
The fewer what is generated in journey is the better.H2, CO gas be the effective fuel of power generation, give one's all in reforming process and be converted into H2, CO to be to improve
Fuel availability.In fuel gas reforming process, the amount of oxygen will affect CO2Generation and tie carbon phenomenon generation.Amount of oxygen
It is big, reform out a large amount of CO2, amount of oxygen is too low, can generate knot carbon.
External fuel cell reformer technologies are suitable only for fixed power supply device, and as mobile fuel cell power source,
Built-in reforming technique must be taken, tubular type SOFC, which has ready conditions, realizes electrode from reformation.
Summary of the invention
A kind of oxygen debt be catalyzed of SOFC tubular type is provided the purpose of the present invention is overcome the deficiencies in the prior art and reforms electrode certainly,
By nickel-base catalyst built in SOFC tubular pole, is generated electricity the heat of itself generation using electrode, fuel is completed in electrode tube
Catalytic reforming, to electrode provide power generation needed for H2, CO, realize SOFC tubular type it is oxygen debt catalysis from reform electrode power generation function
Energy.
It in order to achieve the above object, the invention is realized in this way, is that a kind of oxygen debt catalysis of SOFC tubular type is electric from reforming
Pole, it is characterised in that including confined gas pipe, porous honeycomb catalyst, electrolyte separation layer cathode layer and anode support electrode
Pipe；Wherein, the anode support electrode pipe be divided into three sections of workspaces be followed successively by from left to right it is anti-from workspace, electrode is reformed
Workspace and vent gas treatment workspace are answered, the length from reformation workspace is the 25% of the length of anode support electrode pipe, institute
State electrode reaction workspace length be anode support electrode pipe length 65%, the length of the vent gas treatment workspace is
The 10% of the length of anode support electrode pipe；In the porous honeycomb catalyst insertion confined gas pipe, the confined gas pipe is embedding
Enter reforming in workspace certainly for anode support electrode pipe, the length of confined gas pipe and the equal length from reformation workspace；Institute
Electrolyte separation layer cathode layer is stated to cover on the electrode reaction workspace of anode support electrode pipe, electrolyte separation layer cathode layer
Length is identical as the length of electrode reaction workspace.
In the technical scheme, the manufacturing method of the confined gas pipe is as follows:
Step 1
Yttria-stabilized zirconia powder is dry-mixed with nickel oxide, obtain mixture A, yttria-stabilized zirconia powder with
The weight ratio of nickel oxide is 1:0.2 ± 0.02；Powder graphite and binder are added in mixture A and mixes, obtains mixture
The volume ratio of B, mixture A and powder graphite is 1:10% ± 2%, the volume ratio of mixture A and binder be 1:0.8% ±
0.03%；The water that volume ratio is 6% ± 0.1% is added in mixture B again and is sufficiently mixed mud and practices, obtains required mud A, so
Mud A extrusion molding is formed afterwards and is managed, pipe suspension is at room temperature and 5-6 hours air-dried, it is then dry through 55 DEG C of -65 DEG C of constant temperature
It is 3-4 hours dry, obtain required pipe；
Step 2
Yttria-stabilized zirconia powder is mixed with binder, obtains mixture C, yttria-stabilized zirconia powder with
The volume ratio of binder be 1:0.6% ± 0.03%, in this step used in yttria-stabilized zirconia powder partial size compared with
The partial size of yttria-stabilized zirconia powder used in step 1 is small by 70%, then it is 150% that volume ratio, which is added, into mixture C
± 0.1% water, and be sufficiently mixed to obtain required slurry；
Step 3
Pipe obtained in step 1 is placed in the obtained slurry of step 2 and dips hanging, hangs wind at room temperature
It is 2-3 hours dry, two to four times repeatedly, obtain the pipe of hanging；
Step 4
The pipe of hanging obtained in step 3 is put into batch-type furnace, batch-type furnace was warming up to through equilibrium in 20-24 hours
1300-1400 DEG C, co-sintering 1.5-2.5 hours at a temperature of 1300-1400 DEG C, obtain confined gas pipe.
In the technical scheme, the manufacturing method of the porous honeycomb catalyst is as follows:
Step 1
It with powder graphite is by volume that 1:50% ± 3% is sufficiently mixed by yttria-stabilized zirconia powder, then
Binder is added for 1:1% ± 0.3% by volume in mixture to be sufficiently mixed, is then added and goes for 8% ± 0.1% by volume again
Ionized water is sufficiently mixed, and mud is practiced into base, and moulded pottery not yet put in a kiln to bake is extruded into tubular base through descaling extrusion press, by pipe to be air-dried at room temperature 2-3 small
When, then through 55-65 DEG C freeze-day with constant temperature 3-4 hours, be put into batch-type furnace, batch-type furnace was warming up to through equilibrium in 20-24 hours
1300-1400 DEG C, co-sintering 1.5-2.5 hours at a temperature of 1300-1400 DEG C, obtain required porous honeycomb ceramic circle
Pipe；
Step 2
By nickel-base catalyst and deionized water hybrid modulation agglutination solution, it is 3wt%- that solid, which contains, in colloidal solution
20wt%；
Step 3
The obtained porous honeycomb ceramic round tube of step 1 is placed in the obtained colloidal solution of step 2 and impregnates 10-
15 minutes, solution is proposed with 0.8-1.2mm/s speed, is air-dried at room temperature 10-24 hours, is then dried at 98-102 DEG C again
It 10-14 hours, repeats the process 2-5 times, so that nickel copper-based catalyst loadings is reached 5wt%-20wt%, then will be loaded with again
The porous honeycomb ceramic round tube of nickel copper-based catalyst is put into box kiln roasting, and the temperature of roasting is 500-550 DEG C, when roasting
Between be 2-3 hours, obtain porous honeycomb catalyst.
In the technical scheme, the porous honeycomb catalyst and confined gas pipe are pressed from the length for reforming workspace and is cut out
It cuts, after smearing ceramic glue respectively on the outer wall of porous honeycomb catalyst and the inner wall of confined gas pipe, then porous honeycomb is urged
Agent is inserted into confined gas pipe；Smear pottery respectively on the outer wall of the confined gas pipe and the inner wall of anode support electrode pipe
After porcelain cement, then will be in confined gas pipe insertion anode support electrode pipe；Confined gas pipe and porous honeycomb catalyst will be loaded with
Anode support electrode pipe is put into batch-type furnace and toasts 1-2 hours, and baking temperature is 110-130 DEG C, then puts it into again box
In electric furnace, roasted 0.8-1.2 hours under 500 DEG C of -800 DEG C of degree.
The present invention compared with prior art the advantages of are as follows: by nickel-base catalyst built in SOFC tubular pole, SOFC is fired
Fuel-cell fuel reformation be built in inside tubular pole, using electrode generate electricity itself generation heat, completed in electrode tube
The catalytic reforming of fuel, H2, CO needed for providing power generation to electrode；It reforms the fuel into solidifying with electrode two big critical functions of power generation
Gather in electrode tube, utmostly intensive tubular type SOFC fuel cell structure, utmostly reduces tubular type SOFC fuel cell
Manufacturing cost, battery weight and volume.
Detailed description of the invention
Fig. 1 is structural schematic diagram of the invention;
Fig. 2 is the left view of Fig. 1.
Specific embodiment
Specific embodiments of the present invention will be further explained with reference to the accompanying drawing.It should be noted that for
The explanation of these embodiments is used to help understand the present invention, but and does not constitute a limitation of the invention.In addition, disclosed below
The each embodiment of the present invention in involved technical characteristic can be combined with each other as long as they do not conflict with each other.
In the present description, the orientation or positional relationship of the instructions such as term " left side " and " right side " is side based on the figure
Position or positional relationship are merely for convenience of the description present invention rather than require the present invention that must be constructed and be grasped with specific orientation
Make, therefore is not considered as limiting the invention.
Embodiment one
It as shown in Figures 1 and 2, is a kind of oxygen debt catalysis of SOFC tubular type from reforming electrode, including confined gas pipe 1, more
Hole honeycomb catalyst 2, electrolyte separation layer cathode layer 3 and anode support electrode pipe 4；Wherein, the anode support electrode pipe 4 is drawn
Be divided into three sections of workspaces, three sections of workspaces respectively be from left to right from reform workspace 41, electrode reaction workspace 42 and
Vent gas treatment workspace 43, the length from reformation workspace 41 are the 25% of the length of anode support electrode pipe 4, the electricity
The length of pole reaction workspace 42 is the 65% of the length of anode support electrode pipe 4, and the length of the vent gas treatment workspace 43 is
The 10% of the length of anode support electrode pipe 4；The porous honeycomb catalyst 2 is embedded in confined gas pipe 1, the confined gas
The insertion anode support electrode pipe 4 of pipe 1 is reformed in workspace 41 certainly, the length of confined gas pipe 1 and reformation workspace 41 certainly
Equal length；3 sets of the electrolyte separation layer cathode layer is on the electrode reaction workspace 42 of anode support electrode pipe 4, electrolysis
The length of matter separation layer cathode layer 3 is identical as the length of electrode reaction workspace 42.
In the present embodiment, the manufacturing method of the confined gas pipe 1 is as follows:
Step 1
Yttria-stabilized zirconia powder is dry-mixed with nickel oxide, obtain mixture A, yttria-stabilized zirconia powder with
The weight ratio of nickel oxide is 1:0.18；Powder graphite and binder are added in mixture A and mixes, obtains mixture B, mixes
The volume ratio of object A and powder graphite is 1:8%, and the volume ratio of mixture A and binder is 1:0.77%；Add in mixture B again
Enter the water that volume ratio is 5.9% and be sufficiently mixed mud to practice, obtains required mud A, then mud A extrusion molding is formed and is managed, it will
Pipe suspension at room temperature and air-dry 5 hours, then through 55 DEG C freeze-day with constant temperature 4 hours, obtain required pipe；
Step 2
Yttria-stabilized zirconia powder is mixed with binder, obtains mixture C, yttria-stabilized zirconia powder with
The volume ratio of binder is 1:0.57%, and the partial size of used yttria-stabilized zirconia powder is compared with step 1 in this step
Used in yttria-stabilized zirconia powder partial size it is small 70%, then it is 149.9% that volume ratio, which is added, into mixture C
Water, and be sufficiently mixed to obtain required slurry；
Step 3
Pipe obtained in step 1 is placed in the obtained slurry of step 2 and dips hanging, hangs wind at room temperature
It is 2 hours dry, four times repeatedly, obtain the pipe of hanging；
Step 4
The pipe of hanging obtained in step 3 is put into batch-type furnace, batch-type furnace is warming up to 1300 through equilibrium in 20 hours
DEG C, co-sintering 2.5 hours, obtains confined gas pipe 1 at a temperature of 1300 DEG C.
In the present embodiment, the manufacturing method of the porous honeycomb catalyst 2 is as follows:
Step 1
Yttria-stabilized zirconia powder is mixed with powder graphite, obtains mixture D, yttria-stabilized zirconia powder
Volume ratio with powder graphite is 1:50%, then binder is added in mixture D and is sufficiently mixed, and obtains mixture E, mixes
The volume ratio of object D and binder is 1:1%；Then the water that volume ratio is 7.9% is added in mixture E and is sufficiently mixed mud and practices,
Required mud B is obtained, mud is extruded into porous honeycomb ceramic round tube, by porous honeycomb ceramic round tube to be air-dried at room temperature 2 small
When, then through 55 DEG C freeze-day with constant temperature 4 hours, be put into batch-type furnace, batch-type furnace is warming up to 1300 DEG C through equilibrium in 20 hours, 1300
Co-sintering 2.5 hours at a temperature of DEG C obtain required porous honeycomb ceramic round tube；
Step 2
By nickel-base catalyst and deionized water hybrid modulation agglutination solution, it is 3wt% that solid, which contains, in colloidal solution；
Step 3
The obtained porous honeycomb ceramic round tube of step 1 is placed in the obtained colloidal solution of step 2 and impregnates 10 points
Clock proposes solution with 0.8mm/s speed, is air-dried at room temperature 10 hours, then dries 14 hours at 98 DEG C again, repeats the process 2
It is secondary, so that nickel copper-based catalyst loadings is reached 5wt%, then again puts the porous honeycomb ceramic round tube for being loaded with nickel copper-based catalyst
Enter box kiln roasting, the temperature of roasting is 500 DEG C, and calcining time is 3 hours, obtains porous honeycomb catalyst 2.
In the present embodiment, the porous honeycomb catalyst 2 and confined gas pipe 1 are pressed cuts out from the length for reforming workspace 41
It cuts, after smearing ceramic glue respectively on the outer wall of porous honeycomb catalyst 2 and the inner wall of confined gas pipe 1, then by porous honeycomb
Catalyst 2 is inserted into confined gas pipe 1；On the outer wall of the confined gas pipe 1 and the inner wall of anode support electrode pipe 4 respectively
After smearing ceramic glue, then will be in the insertion anode support electrode pipe 4 of confined gas pipe 1；Confined gas pipe 1 and porous honeycomb will be loaded with
The anode support electrode pipe 4 of catalyst 2 is put into batch-type furnace and toasts 1 hour, and baking temperature is 130 DEG C, then puts it into case again
In formula electric furnace, roasted 1.2 hours under 500 DEG C of degree.
Embodiment two
It as shown in Figures 1 and 2, is a kind of oxygen debt catalysis of SOFC tubular type from reforming electrode, including confined gas pipe 1, more
Hole honeycomb catalyst 2, electrolyte separation layer cathode layer 3 and anode support electrode pipe 4；Wherein, the anode support electrode pipe 4 is drawn
Be divided into three sections of workspaces, three sections of workspaces respectively be from left to right from reform workspace 41, electrode reaction workspace 42 and
Vent gas treatment workspace 43, the length from reformation workspace 41 are the 25% of the length of anode support electrode pipe 4, the electricity
The length of pole reaction workspace 42 is the 65% of the length of anode support electrode pipe 4, and the length of the vent gas treatment workspace 43 is
The 10% of the length of anode support electrode pipe 4；The porous honeycomb catalyst 2 is embedded in confined gas pipe 1, the confined gas
The insertion anode support electrode pipe 4 of pipe 1 is reformed in workspace 41 certainly, the length of confined gas pipe 1 and reformation workspace 41 certainly
Equal length；3 sets of the electrolyte separation layer cathode layer is on the electrode reaction workspace 42 of anode support electrode pipe 4, electrolysis
The length of matter separation layer cathode layer 3 is identical as the length of electrode reaction workspace 42.
In the present embodiment, the manufacturing method of the confined gas pipe 1 is as follows:
Step 1
Yttria-stabilized zirconia powder is dry-mixed with nickel oxide, obtain mixture A, yttria-stabilized zirconia powder with
The weight ratio of nickel oxide is 1:0.22；Powder graphite and binder are added in mixture A and mixes, obtains mixture B, mixes
The volume ratio of object A and powder graphite is 1:12%, and the volume ratio of mixture A and binder is 1:0.83%；Add in mixture B again
Enter the water that volume ratio is 6.1% and be sufficiently mixed mud to practice, obtains required mud A, then mud A extrusion molding is formed and is managed, it will
Pipe suspension at room temperature and air-dry 6 hours, then through 65 DEG C freeze-day with constant temperature 3 hours, obtain required pipe；
Step 2
Yttria-stabilized zirconia powder is mixed with binder, obtains mixture C, yttria-stabilized zirconia powder with
The volume ratio of binder is 1:0.63%, and the partial size of used yttria-stabilized zirconia powder is compared with step 1 in this step
Used in yttria-stabilized zirconia powder partial size it is small 70%, then it is 150.1% that volume ratio, which is added, into mixture C
Water, and be sufficiently mixed to obtain required slurry；
Step 3
Pipe obtained in step 1 is placed in the obtained slurry of step 2 and dips hanging, hangs wind at room temperature
It is 3 hours dry, two times repeatedly, obtain the pipe of hanging；
Step 4
The pipe of hanging obtained in step 3 is put into batch-type furnace, batch-type furnace is warming up to 1400 through equilibrium in 24 hours
DEG C, co-sintering 1.5 hours, obtains confined gas pipe 1 at a temperature of 1400 DEG C.
In the present embodiment, the manufacturing method of the porous honeycomb catalyst 2 is as follows:
Step 1
With powder graphite by volume it is that 1:47% is sufficiently mixed by yttria-stabilized zirconia powder, then presses body
Product adds the deionized water that volume ratio is 8.1% and is sufficiently mixed than being that 1:0.7% is added and binder and is sufficiently mixed, mud practice at
Moulded pottery not yet put in a kiln to bake is extruded into tubular base through descaling extrusion press by base, and pipe is being air-dried at room temperature 3 hours, then small through 65 DEG C of freeze-day with constant temperature 3
When, it is put into batch-type furnace, batch-type furnace is warming up to 1400 DEG C through equilibrium in 24 hours, and co-sintering 1.5 hours, obtains at a temperature of 1400 DEG C
To required porous honeycomb ceramic round tube；
Step 2
By nickel-base catalyst and deionized water hybrid modulation agglutination solution, it is 20wt% that solid, which contains, in colloidal solution；
Step 3
The obtained porous honeycomb ceramic round tube of step 1 is placed in the obtained colloidal solution of step 2 and impregnates 15 points
Clock proposes solution with 1.2mm/s speed, is air-dried at room temperature 4 hours, then dries 10 hours at 102 DEG C again, repeats the process 5
It is secondary, so that nickel copper-based catalyst loadings is reached 20wt%, then again puts the porous honeycomb ceramic round tube for being loaded with nickel copper-based catalyst
Enter box kiln roasting, the temperature of roasting is 550 DEG C, and calcining time is 2 hours, obtains porous honeycomb catalyst 2.
In the present embodiment, the porous honeycomb catalyst 2 and confined gas pipe 1 are pressed from the length for reforming workspace 41
It cuts, after smearing ceramic glue respectively on the outer wall of porous honeycomb catalyst 2 and the inner wall of confined gas pipe 1, then by porous bee
Nest catalyst 2 is inserted into confined gas pipe 1；Divide on the outer wall of the confined gas pipe 1 and the inner wall of anode support electrode pipe 4
Tu Mo not be after ceramic glue, then confined gas pipe 1 is inserted into anode support electrode pipe 4；Confined gas pipe 1 and porous bee will be loaded with
The anode support electrode pipe 4 of nest catalyst 2 is put into batch-type furnace and toasts 2 hours, and baking temperature is 110 DEG C, then puts it into again
In cabinet-type electric furnace, roasted 0.8 hour under 800 DEG C of degree.
Embodiment three
It as shown in Figures 1 and 2, is a kind of oxygen debt catalysis of SOFC tubular type from reforming electrode, including confined gas pipe 1, more
Hole honeycomb catalyst 2, electrolyte separation layer cathode layer 3 and anode support electrode pipe 4；Wherein, the anode support electrode pipe 4 is drawn
Be divided into three sections of workspaces, three sections of workspaces respectively be from left to right from reform workspace 41, electrode reaction workspace 42 and
Vent gas treatment workspace 43, the length from reformation workspace 41 are the 25% of the length of anode support electrode pipe 4, the electricity
The length of pole reaction workspace 42 is the 65% of the length of anode support electrode pipe 4, and the length of the vent gas treatment workspace 43 is
The 10% of the length of anode support electrode pipe 4；The porous honeycomb catalyst 2 is embedded in confined gas pipe 1, the confined gas
The insertion anode support electrode pipe 4 of pipe 1 is reformed in workspace 41 certainly, the length of confined gas pipe 1 and reformation workspace 41 certainly
Equal length；3 sets of the electrolyte separation layer cathode layer is on the electrode reaction workspace 42 of anode support electrode pipe 4, electrolysis
The length of matter separation layer cathode layer 3 is identical as the length of electrode reaction workspace 42.
In the present embodiment, the manufacturing method of the confined gas pipe 1 is as follows: the manufacturing method of the confined gas pipe 1
It is as follows:
Step 1
Yttria-stabilized zirconia powder is dry-mixed with nickel oxide, obtain mixture A, yttria-stabilized zirconia powder with
The weight ratio of nickel oxide is 1:0.2；Powder graphite and binder are added in mixture A and mixes, obtains mixture B, mixes
The volume ratio of object A and powder graphite is 1:10%, and the volume ratio of mixture A and binder is 1:0.8%；Add in mixture B again
Enter the water that volume ratio is 6% and be sufficiently mixed mud to practice, obtains required mud A, then mud A extrusion molding is formed and is managed, will be managed
Suspension at room temperature and air-dry 5.5 hours, then through 60 DEG C freeze-day with constant temperature 3.5 hours, obtain required pipe；
Step 2
Yttria-stabilized zirconia powder is mixed with binder, obtains mixture C, yttria-stabilized zirconia powder with
The volume ratio of binder is 1:0.6%, and the partial size of used yttria-stabilized zirconia powder is compared in step 1 in this step
The partial size of used yttria-stabilized zirconia powder is small by 70%, then the water that volume ratio is 150% is added into mixture C, and
It is sufficiently mixed to obtain required slurry；
Step 3
Pipe obtained in step 1 is placed in the obtained slurry of step 2 and dips hanging, hangs wind at room temperature
It is 2.5 hours dry, three times repeatedly, obtain the pipe of hanging；
Step 4
The pipe of hanging obtained in step 3 is put into batch-type furnace, batch-type furnace is warming up to 1350 through equilibrium in 22 hours
DEG C, co-sintering 2 hours, obtains confined gas pipe 1 at a temperature of 1350 DEG C.
In the present embodiment, the manufacturing method of the porous honeycomb catalyst 2 is as follows:
Step 1
With powder graphite by volume it is that 1:53% is sufficiently mixed by yttria-stabilized zirconia powder, then presses body
Product than being that 1:1.3% addition binder is sufficiently mixed, then is sufficiently mixed by volume for 8% addition deionized water, practice into base, mud by mud
Base is extruded into circular pipe blank through descaling extrusion press, and circular pipe blank is being air-dried at room temperature 2.5 hours, then small through 60 DEG C of freeze-day with constant temperature 3.5
When, it is put into batch-type furnace, batch-type furnace is warming up to 1350 DEG C through equilibrium in 22 hours, and co-sintering 2 hours, obtains at a temperature of 1350 DEG C
Required porous honeycomb ceramic round tube；
Step 2
By nickel-base catalyst and deionized water hybrid modulation agglutination solution, it is 11wt% that solid, which contains, in colloidal solution；
Step 3
The obtained porous honeycomb ceramic round tube of step 1 is placed in the obtained colloidal solution of step 2 and impregnates 12 points
Clock is air-dried at room temperature 17 hours, is then dried 12 hours at 100 DEG C again, repeated the process 3 times with 1mm/s speed proposition solution,
So that nickel copper-based catalyst loadings is reached 12wt%, is then again put into the porous honeycomb ceramic round tube for being loaded with nickel copper-based catalyst
Box kiln roasting, the temperature of roasting are 520 DEG C, and calcining time is 2.5 hours, obtain porous honeycomb catalyst 2.
In the present embodiment, the porous honeycomb catalyst 2 and confined gas pipe 1 are pressed from the length for reforming workspace 41
It cuts, after smearing ceramic glue respectively on the outer wall of porous honeycomb catalyst 2 and the inner wall of confined gas pipe 1, then by porous bee
Nest catalyst 2 is inserted into confined gas pipe 1；Divide on the outer wall of the confined gas pipe 1 and the inner wall of anode support electrode pipe 4
Tu Mo not be after ceramic glue, then confined gas pipe 1 is inserted into anode support electrode pipe 4；Confined gas pipe 1 and porous bee will be loaded with
The anode support electrode pipe 4 of nest catalyst 2 is put into batch-type furnace and toasts 1.5 hours, and baking temperature is 120 DEG C, is then put again
Enter in cabinet-type electric furnace, is roasted 1 hour under 650 DEG C of degree.
Embodiments of the present invention are explained in detail in conjunction with attached drawing above, but the present invention is not limited to described reality
Apply mode.For the ordinary skill in the art, without departing from the principle and spirit of the present invention to these
Embodiment carries out a variety of variations, modification, replacement and deformation and still falls within the scope of the present invention.
Claims (3)
1. electrode, including confined gas pipe (1), porous honeycomb catalyst (2), electrolysis are reformed in a kind of oxygen debt catalysis of SOFC tubular type certainly
Matter separation layer cathode layer (3) and anode support electrode pipe (4)；Wherein, the anode support electrode pipe (4) is divided into three sections of work
Area is followed successively by from left to right from reformation workspace (41), electrode reaction workspace (42) and vent gas treatment workspace (43), institute
State 25% from the length that the length for reforming workspace (41) is anode support electrode pipe (4), the electrode reaction workspace (42)
Length be anode support electrode pipe (4) length 65%, the length of the vent gas treatment workspace (43) is anode-supported electricity
The 10% of the length of pole pipe (4)；In porous honeycomb catalyst (2) insertion confined gas pipe (1), the confined gas pipe (1)
Insertion anode support electrode pipe (4) is reformed in workspace (41) certainly, the length of confined gas pipe (1) and reformation workspace certainly
(41) equal length；The electrolyte separation layer cathode layer (3) covers in the electrode reaction workspace of anode support electrode pipe (4)
(42) on, the length of electrolyte separation layer cathode layer (3) is identical as the length of electrode reaction workspace (42)；It is characterized in that institute
The manufacturing method for stating confined gas pipe (1) is as follows:
Step 1
Yttria-stabilized zirconia powder is dry-mixed with nickel oxide, obtain mixture A, yttria-stabilized zirconia powder and oxidation
The weight ratio of nickel is 1:0.2 ± 0.02；Powder graphite and binder are added in mixture A and mixes, obtains mixture B, mixes
The volume ratio of object A and powder graphite is closed as 1:10% ± 2%, the volume ratio of mixture A and binder is 1:0.8% ± 0.03%；Again
The water that volume ratio is 6% ± 0.1% is added in mixture B and is sufficiently mixed mud and practices, required mud A is obtained, then by mud A
Extrusion molding forms pipe, and pipe suspension is at room temperature and 5-6 hours air-dried, then small through 55 DEG C of -65 DEG C of freeze-day with constant temperature 3-4
When, obtain required pipe；
Step 2
Yttria-stabilized zirconia powder is mixed with binder, obtains mixture C, yttria-stabilized zirconia powder and bonding
The volume ratio of agent is 1:0.6% ± 0.03%, and the partial size of used yttria-stabilized zirconia powder is compared with step in this step
The partial size of yttria-stabilized zirconia powder used in one is small by 70%, then into mixture C be added volume ratio be 150% ±
0.1% water, and be sufficiently mixed to obtain required slurry；
Step 3
Pipe obtained in step 1 is placed in the obtained slurry of step 2 and dips hanging, suspension air-dries at room temperature
2-3 hours, two to four times repeatedly, obtain the pipe of hanging；
Step 4
The pipe of hanging obtained in step 3 is put into batch-type furnace, batch-type furnace was warming up to through equilibrium in 20-24 hours
1300-1400 DEG C, co-sintering 1.5-2.5 hours at a temperature of 1300-1400 DEG C, obtain confined gas pipe (1).
2. electrode is reformed in the oxygen debt catalysis of SOFC tubular type according to claim 1 certainly, it is characterised in that the porous honeycomb catalysis
The manufacturing method of agent (2) is as follows:
Step 1
With powder graphite by volume it is that 1:50% ± 3% is sufficiently mixed by yttria-stabilized zirconia powder, then mixes
Binder is added for 1:1% ± 0.3% by volume in object to be sufficiently mixed, deionization then is added for 8% ± 0.1% by volume again
Water is sufficiently mixed, and mud is practiced into base, and moulded pottery not yet put in a kiln to bake is extruded into tubular base through descaling extrusion press, by pipe to be air-dried at room temperature 2-3 small
When, then through 55-65 DEG C freeze-day with constant temperature 3-4 hours, be put into batch-type furnace, batch-type furnace was warming up to through equilibrium in 20-24 hours
1300-1400 DEG C, co-sintering 1.5-2.5 hours at a temperature of 1300-1400 DEG C, obtain required porous honeycomb ceramic circle
Pipe；
Step 2
By nickel-base catalyst and deionized water hybrid modulation agglutination solution, it is 3wt%-20wt% that solid, which contains, in colloidal solution；
Step 3
The obtained porous honeycomb ceramic round tube of step 1 is placed in the obtained colloidal solution of step 2 and impregnates 10-15 points
Clock proposes solution with 0.8-1.2mm/s speed, is air-dried at room temperature 10-24 hours, then dries 10-14 at 98-102 DEG C again
Hour, it repeats step 2-5 times, so that nickel copper-based catalyst loadings is reached 5wt%-20wt%, then will be loaded with nickel copper-based again and urge
The porous honeycomb ceramic round tube of agent is put into box kiln roasting, and the temperature of roasting is 500-550 DEG C, calcining time 2-3
Hour, obtain porous honeycomb catalyst (2).
3. electrode is reformed in the oxygen debt catalysis of SOFC tubular type according to claim 1 certainly, it is characterised in that by the porous honeycomb
Catalyst (2) and confined gas pipe (1) are pressed to be cut from the length for reforming workspace (41), in the outer of porous honeycomb catalyst (2)
After smearing ceramic glue respectively on the inner wall of wall and confined gas pipe (1), then by porous honeycomb catalyst (2) be inserted into confined gas pipe
(1) in；After smearing ceramic glue respectively on the outer wall of the confined gas pipe (1) and the inner wall of anode support electrode pipe (4), then
It will be in confined gas pipe (1) insertion anode support electrode pipe (4)；Confined gas pipe (1) and porous honeycomb catalyst (2) will be loaded with
Anode support electrode pipe (4) be put into batch-type furnace toast 1-2 hour, baking temperature be 110-130 DEG C, then put it into again
In cabinet-type electric furnace, roasted 0.8-1.2 hours under 500 DEG C of -800 DEG C of degree.
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