CN108736024A - A kind of fuel cell system reformer chamber and fuel cell system - Google Patents
A kind of fuel cell system reformer chamber and fuel cell system Download PDFInfo
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- CN108736024A CN108736024A CN201810569926.0A CN201810569926A CN108736024A CN 108736024 A CN108736024 A CN 108736024A CN 201810569926 A CN201810569926 A CN 201810569926A CN 108736024 A CN108736024 A CN 108736024A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
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- 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
- H01M8/0618—Reforming processes, e.g. autothermal, partial oxidation or steam reforming
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of fuel cell system reformer chamber and fuel cell systems, reformer chamber includes almag flow-field plate and Seal end plate, almag flow-field plate includes flow field, composite catalyst and complex carrier, complex carrier is formed on the surface in flow field, complex carrier is made of aluminium oxide and magnesia, composite catalyst is formed on complex carrier, composite catalyst is made of copper simple substance, copper oxide, germanium dioxide and indium sesquioxide, complex carrier is formed by electrochemical erosion method, and composite catalyst is formed by reactive plasma spray coating method and cold metallikon.The reformer chamber of the present invention has high methanol conversion ratio and low CO selection rates, the also ability with the poisoning of good resisting sulfide.
Description
Technical field
The present invention relates to a kind of fuel cell system reformer chamber and fuel cell systems, and in particular to a kind of methanol-water weight
The fuel cell system reformer chamber and fuel cell system of whole hydrogen manufacturing.
Background technology
Fuel cell water hydrogen generator is converted into hydrogen using methanol-water as fuel, methanol-water, is passed through fuel cell progress
Chemical energy is converted into electric energy by electrochemical reaction, and energy conversion efficiency higher only discharges water and a small amount of carbon dioxide,
PM2.5 discharges are 0, realize real environmental protection.Solve the problems, such as Hydrogen Energy " storage and transportation is difficult, of high cost ".With traditional vapour
Oil/diesel-driven generator is compared, and has efficient, stable lasting power generation；Pollution-free, environmentally protective；Low decibel, zero noise pollution；Exempt from
It safeguards, the advantage of low running cost.The service life of water hydrogen power generator is up to 10 years or more, and product has reliable and stable set
Standby service ability and security protection ability, can long-time steady operation, uninterrupted power supply is provided.
Methanol-water is after gasification system gasification is gas, and catalytic reforming is hydrogen in reformer chamber.Therefore, methanol-water weight
Whole hydrogen producing technology more becomes the hot spot researched and developed both at home and abroad, and technological core is the preparation of methanol-water reforming hydrogen-production catalyst.
The activity and selectivity that Pd/ZnO alloy catalysts have had in hydrogen production from methanol-steam reforming at present, but Pd is expensive, warp
Ji property is poor, and anti-impurity poisoning capability is weaker.Base metal Cu bases catalyst and other oxide catalysts are cheap, tool
There is preferable methanol conversion, but CO is selectively poor, anti-impurity poisoning is also poor, and stability problem is relatively difficult to resolve certainly.And first
Common impurity has sulfide, chloride etc. in alcohol.
Therefore, at present the research emphasis of reforming catalyst from improving methanol conversion and H2Selectivity, how be changed into has
Effect reduces the selectivity and resisting sulfide, chloride poisoning of CO.
Invention content
For this purpose, a kind of fuel cell system reformer chamber of present invention proposition and fuel cell system, it is therefore an objective to solve methanol
The resisting sulfide of water reforming hydrogen-production catalyst is poisoned bad problem.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：A kind of fuel cell system reformer chamber,
Including almag flow-field plate and Seal end plate, almag flow-field plate includes flow field, composite catalyst and complex carrier, spy
Sign is that complex carrier is formed on the surface in flow field, and complex carrier is made of aluminium oxide and magnesia, and composite catalyst is formed
On complex carrier, composite catalyst is made of copper simple substance, copper oxide, germanium dioxide and indium sesquioxide.
Preferably, complex carrier is formed by electrochemical erosion method.Electrochemical erosion method includes following step successively：To have
After the surface of the almag plate in flow field is cleaned with deionized water, electrochemical corrosion is carried out, the almag plate after corrosion is used
Ethyl alcohol and deionized water are cleaned successively, are then placed in baking oven dry.
Preferably, composite catalyst is formed by reactive plasma spray coating method and cold metallikon.Reactive plasma is sprayed
Coating includes following step successively：By copper powder, indium powder, germanium powder in mass ratio 1:0.5-3:0.5-3 is mixed after mixing
Mixed powder is put into the powder feeder of plasma-spraying device by powder, using the dry almag plate through excessive erosion as substrate,
Choose Ar and O2As spray gas, by plasma-spraying device the dry almag plate surface through excessive erosion into
Row plasma spraying is prepared in the runner of the dry almag plate through excessive erosion by copper oxide, indium oxide and oxidation
The three-way catalyst of germanium composition.
Preferably, composite catalyst is formed by reactive plasma spray coating method and cold metallikon.Cold metallikon includes such as
Under step successively：Copper powder is put into cold spraying plating equipment, using the almag plate with three-way catalyst as substrate, chooses N2Make
For working gas, cold spraying plating is carried out in the almag plate surface with three-way catalyst by cold spraying plating equipment, with three
Composite catalyst is prepared in the runner of the almag plate of first catalyst.
Preferably, complex carrier is formed by electrochemical erosion method.The technique of electrochemical erosion method is as follows：With sodium chloride solution
As electrolyte, for the almag plate with flow field as anode, graphite cake applies direct current, electric current at room temperature as cathode
Density is 100~300A/m2, voltage 200-300V, the electrochemical corrosion time be 10~120mins.
Preferably, composite catalyst is formed by reactive plasma spray coating method and cold metallikon.Reactive plasma is sprayed
The technique of coating is as follows：The flow of Ar is 50-90L/min, O2Flow be 10-25L/min, the electricity of plasma-spraying device
Arc voltage is 40-50V, arc current 800-900A, send mixed powder speed 15-50g/min, spray distance 80-135mm, powder feeding
50 ° -90 ° of angle.
Preferably, composite catalyst is formed by reactive plasma spray coating method and cold metallikon.The technique of cold metallikon
It is as follows：Injection pressure is 1-3MPa, and injection temperation is 25-80 DEG C, gas velocity 1-2m3.min-1, copper powder conveying speed 5-
15kg.h-1, jet length 10-50mm, power 5-25kW.
The present invention also provides a kind of fuel cell systems, including, the fuel cell system reformation of gasifier, the present invention
Room, hydrogen purifier and fuel cell.
The present invention has the following advantages：
1, the present invention is formed using novel processing step --- electrochemical erosion method --- in the runner of almag plate
The complex carrier being made of aluminium oxide and magnesia, the complex carrier generate collaboration together with the composite catalyst of the present invention and make
With, it can be in the case of high methanol conversion ratio and low CO selection rates, the ability with the poisoning of good resisting sulfide.
2, the present invention uses novel processing step --- reactive plasma spray coating method and the novel preparation side of cold metallikon
Method --- the composite catalyst being made of copper simple substance, copper oxide, germanium dioxide and indium sesquioxide is formd, the composite catalyst
Synergistic effect is generated with together with the complex carrier that electrochemical corrosion is formed, there is high methanol conversion ratio and low CO selection rates, also have
There is the ability of good resisting sulfide poisoning.
Description of the drawings
Fig. 1 is the structural schematic diagram of fuel cell system reformer chamber of the present invention.
Fig. 2 is the structural schematic diagram of the cross section in flow field in the almag flow-field plate in Fig. 1.
Fig. 3 is the structural schematic diagram of fuel cell system of the present invention.
Fig. 4 is the preparation technology flow chart of the fuel cell system reformer chamber of the present invention.
Specific implementation mode
With reference to the accompanying drawings to invention is more fully described, wherein illustrating exemplary embodiment of the present invention.
As depicted in figs. 1 and 2, fuel cell system reformer chamber includes almag flow-field plate 1 and Seal end plate 2, aluminium
Magnesium alloy flow-field plate 1 includes flow field 11, composite catalyst 12 and complex carrier 13, and complex carrier 13 is formed in the surface in flow field 11
On, complex carrier 13 is made of aluminium oxide and magnesia, and composite catalyst 12 is formed on complex carrier 13, composite catalyst 12
It is made of copper simple substance, copper oxide, germanium dioxide and indium sesquioxide.Flow field 11, composite catalyst 12 and complex carrier 13 in Fig. 2
Between size be not offered as the relative size between them, be only to illustrate this three.The four of almag flow-field plate 1
A angle has mounting hole, for being installed with Seal end plate 2.Seal end plate 2 has methanol steam air inlet 21 and reforms
Gas gas outlet 22, and also there is mounting hole at four angles of Seal end plate 2, for the mounting hole with almag flow-field plate 1
Alignment installation.Installation method is unlimited, and bolt may be used and installed.
As shown in figure 3, fuel cell system 3 includes gasifier 31, fuel cell system reformer chamber 32, hydrogen purifier
33, fuel cell 34.Raw material is methanol aqueous solution, is gasified after entering vaporizer 31, and fuel cell system use is then passed to
Reformer chamber 32.It obtains reforming gas after reformation, reforms gas and enter after hydrogen purifier 33, obtain high-purity hydrogen.High-purity hydrogen
Into generating electricity in fuel cell.Gas in the prior art may be used in gasifier 31, hydrogen purifier 33, fuel cell 34
Makeup sets, hydrogen purification apparatus and fuel-cell device.
As shown in figure 4, the manufacturing method of fuel cell system reformer chamber is as follows：The magnalium with flow field is chosen first to close
Golden plate after cleaning on the surface of the almag plate with flow field with deionized water, carries out electrochemical corrosion, by the aluminium after corrosion
Magnesium alloy plate ethyl alcohol and deionized water are cleaned successively, are then placed in baking oven dry.
Almag plate with flow field can be with conventional aluminium magnesium alloy plate by being stamped and formed out flow field.The type of runner and
Size is not particularly limited.It may be used snakelike etc..Common almag is mainly made of aluminium and magnesium, and wherein the content of magnesium is 8-
13wt%.The size of almag plate is unlimited, such as (length) 20mm × 30mm × 15mm, 30cm × 50cm × 20cm.
The technique of electrochemical erosion method is as follows：Using sodium chloride solution as electrolyte, the almag plate with flow field is as anode, stone
Black plate applies direct current at room temperature as cathode, and current density is 100~300A/m2, voltage 200-300V, electrochemistry is rotten
The erosion time is 10~120mins.By the almag plate after corrosion with ethyl alcohol clean and deionized water clean successively, ethyl alcohol it is dense
Degree is in 95kWt% or more, and wash number is unlimited, generally 3 times.It is finally putting into baking oven dry.It is dry to may be used very
Sky is dry, and temperature is 60~80 DEG C, and the time is 1~3h.
By copper powder, indium powder, germanium powder in mass ratio 1:0.5-3:0.5-3 obtains mixed powder after mixing, is put into plasma
The powder feeder of body spraying equipment.Copper powder, indium powder, germanium powder quality can be adjusted according to the catalyst thickness of acquisition, copper powder,
Indium powder, germanium powder average diameter D50 be 0.05-0.3 μm.Using the dry almag plate through excessive erosion as substrate, choose
Ar and O2As spray gas, carried out in the dry almag plate surface through excessive erosion by plasma-spraying device etc.
Plasma spray is prepared in the runner of the dry almag plate through excessive erosion by copper oxide, indium oxide and germanium oxide group
At three-way catalyst.There are many ways to mixing, such as colter mixer, spiral ribbon mixer, Agravicmixer, V-type are mixed
Conjunction machine, double-spiral conical mixer, high low-velocity liquid mixer, planetary power mixing machine etc..As long as mixture is uniformly mixed
?.Incorporation time can determines according to actual conditions, usually in 2-10h.Plasma-spraying device uses
SluzerMetco9MC plasma spraying equipments carry out plasma spraying, spray gun type 9MB.In spraying process, the flow of Ar
For 50-90L/min, O2Flow be 10-25L/min, the arc voltage of plasma-spraying device is 40-50V, arc current
800-900A send mixed powder speed 15-50g/min, spray distance 80-135mm, 50 ° -90 ° of powder feeding angle.In spraying process
In, matrix is cooled down using air blowing method or recirculated water cooling method.It is cold when cooling down matrix using air blowing method
But the flow of gas is 100-2000L/min；When cooling down matrix using recirculated water cooling method, the flow of cooling water is 10-
500L/min.The three-way catalyst layer thickness of formation is 1-5 μm.Copper, indium powder, germanium powder are during plasma spray coating
It is aoxidized, forms the very high three-way catalyst of catalytic activity, and can closely be tied with the complex carrier in almag plate runner
It closes, forms the strong catalyst of resisting sulfide ability.
Copper powder is put into cold spraying plating equipment, using the almag plate with three-way catalyst as substrate, chooses N2As
Working gas carries out cold spraying plating, with ternary by cold spraying plating equipment in the almag plate surface with three-way catalyst
Composite catalyst is prepared in the runner of the almag plate of catalyst.The quality of copper powder can be according to the catalyst thickness of acquisition
It is adjusted, the technique of cold metallikon is as follows：Injection pressure is 1-3MPa, and injection temperation is 25-80 DEG C, gas velocity 1-
2m3.min-1, copper powder conveying speed 5-15kg.h-1, jet length 10-50mm, power 5-25kW.The copper catalysis oxidant layer of formation
Thickness is 1-3 μm.Elemental copper will not be oxidized in cold metallization process, avoid decomposition, the problems such as phase transformation, crystal grain are grown up,
The composite catalyst of the present invention is together constituted with three-way catalyst.The composite catalyst of the present invention can carried with complex carrier
In the case of high methanol conversion ratio and reduction CO selection rates, the ability of resisting sulfide is improved.
Almag flow-field plate with composite catalyst and complex carrier is assembled, around uses Seal end plate close
Envelope, is assembled into fuel cell system reformer chamber.Successively by gasifier, reformer chamber, hydrogen purifier and fuel cell of the invention
It is attached and assembles, form the fuel cell system of the present invention.The fuel cell system operation principle of the present invention is as follows：Water hydrogen
Raw material uses methanol-water, the i.e. mixed solution of first alcohol and water.Methanol-water is passed through in gasifier, first alcohol and water is passed through after being gasified
Reformer chamber.By catalytic reforming, obtain reforming gas.It reforms gas to be purified in hydrogen purifier, obtains high-purity hydrogen, be supplied to
It generates electricity in fuel cell.
The present invention is with hydrogen content (%), carbon monoxide selective (%), methanol conversion (%) in reformation gas to this hair
Bright fuel cell is assessed with reformer chamber.Using dress, there are four the Agilent 3000A in channel and four TCD detectors
Micro gas chromatography system (GC) are monitored and are analyzed.Whole system is automatic, and uses calculating
Machine is acquired to control with carrying out operation and data.
H containing 0.1wt% in the methanol of test2S, reformer chamber run 5h after, test reform gas in hydrogen content (%),
Carbon monoxide selective (%), methanol conversion (%).
The present invention is described in detail below in conjunction with embodiment.
Embodiment 1
Choose the almag plate of 30cm × 50cm with flow field × 10cm of 8wt%, runner depth 1cm, wide 1cm, ridge
Width is 1cm.With after ethyl alcohol, deionized water successively supersonic oscillations 5min after almag plate is cleaned up, then configure
The sodium chloride solution of 0.1mol/L uses graphite as cathode as electrolyte solution, and almag plate is applied at room temperature as anode
Add direct current, current density 100A/m2, voltage 200V, the electrochemical corrosion time be 120mins.By the magnalium after corrosion
Alloy sheets are cleaned with ethyl alcohol and deionized water is cleaned 3 times successively.It is put into baking oven and is dried in vacuo, temperature is 60 DEG C, and the time is 3h.
By copper powder, indium powder, germanium powder in mass ratio 1:1:Mixed powder is obtained after 1 mixing 2h, is put into plasma-spraying device
Powder feeder.Copper powder, indium powder, germanium powder average diameter D50 be 0.1 μm.Using the dry almag plate through excessive erosion as
Substrate chooses Ar and O2As spray gas, by plasma-spraying device in the dry almag plate through excessive erosion
Surface carries out plasma spraying, is prepared by copper oxide, indium oxide in the runner of the dry almag plate through excessive erosion
With the three-way catalyst of germanium oxide composition.The flow of Ar is 50L/min, O2Flow be 10L/min, plasma-spraying device
Arc voltage be 40V, arc current 800A, mixed powder powder feed rate 15g/min, spray distance 80mm, 50 ° of powder feeding angle.
It is 2 μm that three-way catalyst layer thickness is obtained in runner.
Copper powder is put into cold spraying plating equipment, using the almag plate with three-way catalyst as substrate, chooses N2As
Working gas carries out cold spraying plating, with ternary by cold spraying plating equipment in the almag plate surface with three-way catalyst
Composite catalyst is prepared in the runner of the almag plate of catalyst.The injection pressure of cold metallikon is 1MPa, injection temperation
It is 25 DEG C, gas velocity 1m3.min-1, copper powder conveying speed 5kg.h-1, jet length 10mm, power 5kW.The copper of formation
Catalyst layer thickness is 1 μm.
Almag flow-field plate with composite catalyst and complex carrier is assembled, around uses Seal end plate close
Envelope, is assembled into fuel cell system reformer chamber.Methanol-water containing hydrogen sulfide is passed through in gasifier, first alcohol and water is gasified
It is passed through middle reformer chamber.By catalytic reforming, obtain reforming gas.
It is 75.8% to measure and reform hydrogen content in gas, carbon monoxide selective 5.1%, and methanol conversion is
98.1%.
Embodiment 2
Choose the almag plate of 30cm × 50cm with flow field × 10cm of 10wt%, runner depth 1cm, wide 1cm, ridge
Width is 1cm.With after ethyl alcohol, deionized water successively supersonic oscillations 5min after almag plate is cleaned up, then configure
The sodium chloride solution of 0.1mol/L uses graphite as cathode as electrolyte solution, and almag plate is applied at room temperature as anode
Add direct current, current density 200A/m2, voltage 250V, the electrochemical corrosion time be 60mins.Magnalium after corrosion is closed
Golden plate is cleaned with ethyl alcohol and deionized water is cleaned 3 times successively.It is put into baking oven and is dried in vacuo, temperature is 70 DEG C, and the time is 2h.
By copper powder, indium powder, germanium powder in mass ratio 1:2:Mixed powder is obtained after 2 mixing 6h, is put into plasma-spraying device
Powder feeder.Copper powder, indium powder, germanium powder average diameter D50 be 0.2 μm.Using the dry almag plate through excessive erosion as
Substrate chooses Ar and O2As spray gas, by plasma-spraying device in the dry almag plate through excessive erosion
Surface carries out plasma spraying, is prepared by copper oxide, indium oxide in the runner of the dry almag plate through excessive erosion
With the three-way catalyst of germanium oxide composition.The flow of Ar is 70L/min, O2Flow be 18L/min, plasma-spraying device
Arc voltage be 45V, arc current 850A, mixed powder powder feed rate 25g/min, spray distance 100mm, 60 ° of powder feeding angle.
It is 3 μm that three-way catalyst layer thickness is obtained in runner.
Copper powder is put into cold spraying plating equipment, using the almag plate with three-way catalyst as substrate, chooses N2As
Working gas carries out cold spraying plating, with ternary by cold spraying plating equipment in the almag plate surface with three-way catalyst
Composite catalyst is prepared in the runner of the almag plate of catalyst.The injection pressure of cold metallikon is 1.5MPa, injection temperature
Degree is 45 DEG C, gas velocity 1.5m3.min-1, copper powder conveying speed 10kg.h-1, jet length 25mm, power 10kW.Shape
At copper catalyst layer thickness be 1.5 μm.
Almag flow-field plate with composite catalyst and complex carrier is assembled, around uses Seal end plate close
Envelope, is assembled into fuel cell system reformer chamber.Methanol-water containing hydrogen sulfide is passed through in gasifier, first alcohol and water is gasified
It is passed through middle reformer chamber.By catalytic reforming, obtain reforming gas.
It is 74.6% to measure and reform hydrogen content in gas, carbon monoxide selective 4.7%, and methanol conversion is
96.7%.
Embodiment 3
Choose the almag plate of 30cm × 50cm with flow field × 10cm of 12wt%, runner depth 1cm, wide 1cm, ridge
Width is 1cm.With after ethyl alcohol, deionized water successively supersonic oscillations 5min after almag plate is cleaned up, then configure
The sodium chloride solution of 0.1mol/L uses graphite as cathode as electrolyte solution, and almag plate is applied at room temperature as anode
Add direct current, current density 300A/m2, voltage 300V, the electrochemical corrosion time be 10mins.Magnalium after corrosion is closed
Golden plate is cleaned with ethyl alcohol and deionized water is cleaned 3 times successively.It is put into baking oven and is dried in vacuo, temperature is 80 DEG C, and the time is 1h.
By copper powder, indium powder, germanium powder in mass ratio 1:3:Mixed powder is obtained after 3 mixing 8h, is put into plasma-spraying device
Powder feeder.Copper powder, indium powder, germanium powder average diameter D50 be 0.3 μm.Using the dry almag plate through excessive erosion as
Substrate chooses Ar and O2As spray gas, by plasma-spraying device in the dry almag plate through excessive erosion
Surface carries out plasma spraying, is prepared by copper oxide, indium oxide in the runner of the dry almag plate through excessive erosion
With the three-way catalyst of germanium oxide composition.The flow of Ar is 80L/min, O2Flow be 25L/min, plasma-spraying device
Arc voltage be 50V, arc current 900A, mixed powder powder feed rate 45g/min, spray distance 120mm, 70 ° of powder feeding angle.
It is 3 μm that three-way catalyst layer thickness is obtained in runner.
Copper powder is put into cold spraying plating equipment, using the almag plate with three-way catalyst as substrate, chooses N2As
Working gas carries out cold spraying plating, with ternary by cold spraying plating equipment in the almag plate surface with three-way catalyst
Composite catalyst is prepared in the runner of the almag plate of catalyst.The injection pressure of cold metallikon is 3MPa, injection temperation
It is 65 DEG C, gas velocity 2m3.min-1, copper powder conveying speed 15kg.h-1, jet length 35mm, power 20kW.It is formed
Copper catalyst layer thickness is 2 μm.
Almag flow-field plate with composite catalyst and complex carrier is assembled, around uses Seal end plate close
Envelope, is assembled into fuel cell system reformer chamber.Methanol-water containing hydrogen sulfide is passed through in gasifier, first alcohol and water is gasified
It is passed through reformer chamber.By catalytic reforming, obtain reforming gas.
It is 74.8% to measure and reform hydrogen content in gas, carbon monoxide selective 5.4%, and methanol conversion is
97.1%.
Comparative example 1
Other than almag plate is replaced with aluminium sheet, remaining is the same as embodiment 1.
It is 51.6% to measure and reform hydrogen content in gas, carbon monoxide selective 15.4%, and methanol conversion is
55.1%.
Comparative example 2
Other than almag plate is replaced with magnesium plate, remaining is the same as embodiment 1.
It is 50.3% to measure and reform hydrogen content in gas, carbon monoxide selective 16.7%, and methanol conversion is
53.2%.
Comparative example 3
Other than indium powder is replaced with zinc powder, remaining is the same as embodiment 1.
It is 41.7% to measure and reform hydrogen content in gas, carbon monoxide selective 20.1%, and methanol conversion is
43.2%.
Comparative example 4
Other than germanium powder is replaced with zinc powder, remaining is the same as embodiment 1.
It is 39.2% to measure and reform hydrogen content in gas, carbon monoxide selective 21.2%, and methanol conversion is
42.3%.
Comparative example 5
Other than reactive plasma spray coating method is replaced with impregnation sintering method, remaining is the same as embodiment 1.
Impregnation sintering method includes following step successively：It weighs mantoquita, germanium salt, indium salts to be dissolved in water as solution, be immersed in dry
On the dry almag plate through excessive erosion, 500-550 DEG C roasts 2-4 hours, is obtained on flow field by copper oxide, germanium dioxide
With the catalyst of indium sesquioxide composition.
It is 48.9% to measure and reform hydrogen content in gas, carbon monoxide selective 13.8%, and methanol conversion is
53.5%.
Can be seen that the fuel cell system reformer chamber of the present invention from embodiment 1-3 can be reasonably resistant to sulfide
Poisoning, and keep methanol conversion and carbon monoxide selective.It can be seen that from comparative example 1-5 in obtained reformer chamber
Sulfide poisoning has occurred in catalyst, and methanol conversion, hydrogen content significantly decline.
The above content is only presently preferred embodiments of the present invention, for those of ordinary skill in the art, according to the present invention
Thought, there will be changes in the specific implementation manner and application range, and the content of the present specification should not be construed as to the present invention
Limitation.
Claims (8)
1. a kind of fuel cell system reformer chamber, including almag flow-field plate and Seal end plate, the almag flow field
Plate includes flow field, composite catalyst and complex carrier, which is characterized in that the complex carrier is formed in the surface in the flow field
On, the complex carrier is made of aluminium oxide and magnesia, and the composite catalyst is formed on the complex carrier, described multiple
Catalyst is closed to be made of copper simple substance, copper oxide, germanium dioxide and indium sesquioxide.
2. fuel cell system reformer chamber according to claim 1, wherein the complex carrier is by electrochemical erosion method
It is formed, the electrochemical erosion method includes following step successively：By the surface deionized water of the almag plate with flow field
After cleaning, carry out electrochemical corrosion, by after corrosion almag plate ethyl alcohol and deionized water clean successively, be then placed in baking
It is dry in case.
3. fuel cell system reformer chamber according to claim 1 or 2, wherein the composite catalyst passes through reaction
Plasma spraying process and cold metallikon are formed, and the reactive plasma spray coating method includes following step successively：By copper powder, indium
Powder, germanium powder in mass ratio 1:0.5-3:0.5-3 obtains mixed powder after mixing, and mixed powder is put into plasma-spraying device
Powder feeder choose Ar and O using the dry almag plate through excessive erosion as substrate2As spray gas, by described
Plasma-spraying device carries out plasma spraying in the almag plate surface through excessive erosion of the drying, in the drying
The almag plate through excessive erosion runner in prepare the three-way catalyst being made of copper oxide, indium oxide and germanium oxide.
4. fuel cell system reformer chamber described in any one of claim 1 to 3, wherein the composite catalyst
It is formed by reactive plasma spray coating method and cold metallikon, the cold metallikon includes following step successively：Copper powder is put into
Cold spraying plating equipment chooses N using the almag plate with three-way catalyst as substrate2As working gas, by described cold
Spraying plating equipment carries out cold spraying plating in the almag plate surface with three-way catalyst, described with three-way catalyst
The composite catalyst is prepared in the runner of almag plate.
5. fuel cell system reformer chamber according to any one of claims 1 to 4, wherein the complex carrier by
Electrochemical erosion method is formed, and the technique of the electrochemical erosion method is as follows：Using sodium chloride solution as electrolyte, with flow field
Almag plate applies direct current at room temperature as anode, graphite cake as cathode, and current density is 100~300A/m2, electricity
Pressure is 200-300V, and the electrochemical corrosion time is 10~120mins.
6. fuel cell system reformer chamber according to any one of claims 1 to 5, wherein the composite catalyst
It is formed by reactive plasma spray coating method and cold metallikon, the technique of the reactive plasma spray coating method is as follows：The stream of Ar
Amount is 50-90L/min, O2Flow be 10-25L/min, the arc voltage of plasma-spraying device is 40-50V, electric arc electricity
800-900A is flowed, mixed powder speed 15-50g/min, spray distance 80-135mm, 50 ° -90 ° of powder feeding angle are sent.
7. according to fuel cell system reformer chamber according to any one of claims 1 to 6, wherein the composite catalyst
It is formed by reactive plasma spray coating method and cold metallikon, the technique of the cold metallikon is as follows：Injection pressure is 1-3MPa,
Injection temperation is 25-80 DEG C, gas velocity 1-2m3.min-1, copper powder conveying speed 5-15kg.h-1, jet length 10-
50mm, power 5-25kW.
8. a kind of fuel cell system, including, gasifier, fuel cell system according to any one of claims 1 to 7 weight
Whole room, hydrogen purifier and fuel cell.
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| CN111326752A (en) * | 2018-12-14 | 2020-06-23 | 中国科学院大连化学物理研究所 | Solid powder of fuel cell catalyst layer and preparation method and application thereof |
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| CN101145617A (en) * | 2006-09-11 | 2008-03-19 | 三星Sdi株式会社 | Reformer for fuel cell, and fuel cell system including same |
| CN102785058A (en) * | 2011-05-18 | 2012-11-21 | 通用电气公司 | components with precision surface channels and hybrid machining method |
| CN102969514A (en) * | 2012-12-03 | 2013-03-13 | 哈尔滨工业大学 | Metal-coated oxide nano core-shell structure catalyst and preparation method thereof |
| CN103949260A (en) * | 2014-05-19 | 2014-07-30 | 哈尔滨工业大学 | Preparation method of surface catalyst for runner in cavity of aluminum alloy miniature methanol reforming chamber |
| CN105428666A (en) * | 2015-11-26 | 2016-03-23 | 福州大学 | Fuel cell catalyst with sulfur dioxide poisoning resistance |
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| CN102785058A (en) * | 2011-05-18 | 2012-11-21 | 通用电气公司 | components with precision surface channels and hybrid machining method |
| CN102969514A (en) * | 2012-12-03 | 2013-03-13 | 哈尔滨工业大学 | Metal-coated oxide nano core-shell structure catalyst and preparation method thereof |
| CN103949260A (en) * | 2014-05-19 | 2014-07-30 | 哈尔滨工业大学 | Preparation method of surface catalyst for runner in cavity of aluminum alloy miniature methanol reforming chamber |
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