CN103165924A - Fuel distribution pipe with functions of fuel gas reformation and waste gas combustion, and application - Google Patents
Fuel distribution pipe with functions of fuel gas reformation and waste gas combustion, and application Download PDFInfo
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- CN103165924A CN103165924A CN2011104135697A CN201110413569A CN103165924A CN 103165924 A CN103165924 A CN 103165924A CN 2011104135697 A CN2011104135697 A CN 2011104135697A CN 201110413569 A CN201110413569 A CN 201110413569A CN 103165924 A CN103165924 A CN 103165924A
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a fuel distribution pipe with functions of fuel gas reformation and waste gas combustion, and a preparation method thereof. The fuel distribution pipe is used for an anode-supported tubular solid oxide fuel cell. The fuel distribution pipe comprises an inert supporting pipe with two ends open. Both the inner wall and the outer wall of the inert supporting pipe are loaded with a catalyst layer; the thickness of the catalyst layer is 5-300 micrometers, and components of the wall layer catalyst comprise, by weight, 20%-70% of Al2O3, 10%-40% of CeO2, 20%-40% of ZrO, 0-20% of La2O3, 0.5%-10% of at least one of alkali metal or alkaline earth metal oxides, 0.01-5.0 % of at least one of platinum metal elements such as ruthenium, rhodium, palladium, osmium, iridium, platinum and the like, and 0.5-15% of at least one elements in the fourth period and the VIII group of the periodic table of elements. An inlet end of the fuel distribution pipe is connected to a public fuel chamber, the outlet of the fuel distribution pipe passes through an anode-supported tubular cell anode cavity; the inner wall catalyst and the outer wall catalyst disposed in the cell anode cavity can catalyze water steam to reform a natural gas, a liquefied petroleum gas and the like to produce a reformed gas for supplying to the anode-supported tubular solid oxide fuel cell for power generation; the outer wall catalyst disposed out of the cell can catalyze a fuel gas to carry out a combustion reaction with the air so as to provide heat energy to the reformation reaction and to the gas of flowing to the cell.
Description
Technical field
The present invention relates to a kind of fuel rail and application thereof with fuel gas reformation and tail gas catalyzed combustion function, this fuel rail can be applicable to the anode-supported cast solid oxide fuel cell power generating system of an end sealing, it is when distributing fuel, the reformation of catalytic fuel gas, the burning of catalytic fuel battery outlet port tail gas, realize simultaneously the thermal coupling of reforming reaction and combustion reaction, cell reaction, improve generating efficiency and system's total energy utilization ratio of system.
Background technology
Solid Oxide Fuel Cell (SOFC) is that a kind of employing soild oxide is as electrolyte membrance, by electrochemical reaction, the chemical energy of fuel is converted into the Blast Furnace Top Gas Recovery Turbine Unit (TRT) of electric energy efficiently, cleanly, its generating efficiency can reach more than 50%, cogeneration efficient higher than 80%, is the novel power generation device that reduces the discharging of carbon dioxide.Solid Oxide Fuel Cell not only can be used hydrogen fuel, can also adopt aboundresources and cheap natural gas, liquefied petroleum gas, fuel oil, town gas and biogas etc. to act as a fuel.
Configuration according to the core component-membrane electrode of Solid Oxide Fuel Cell or monocell is different, and Solid Oxide Fuel Cell can be divided into tubular cells, plate shaped battery and monolithic devices battery.Supporter according to membrane electrode or battery is different, and Solid Oxide Fuel Cell can be divided into electrolyte-supporting type, cathode support type and anode support type.The battery of different battery configuration and type is different with the modular construction that electric power station system adopts in the structure battery pile, and the mode of structure is also different, and the structure in battery pile and power station is also different.In various types of batteries, with the technology of the cathode support tubular solid oxide fuel cells technical development of U.S. Siemens-Westinghouse Electric and the battery technology comparative maturity of electrolyte-supported, both the working temperature of battery is all more than 900C.And the anode supported cells technology be domestic inside and outside in the last few years research and development battery technology, the working temperature of battery is at 650-800C.
As previously mentioned, natural gas etc. are the fuel of Solid Oxide Fuel Cell, and Solid Oxide Fuel Cell can improve the utilization ratio of natural gas.But, directly natural gas is led to the anode of solid oxide fuel cell reaction and can cause the anode carbon deposit, and then the interface of break current conduction, the performance of reduction eelctro-catalyst affects the gas transfer in electrode, reduces battery life.Therefore, in electricity generation system, the fuel such as natural gas are first generally synthesis gas through the water vapour catalytic reforming, then carry out electrochemical reaction on galvanic anode.
Fuel reforming reaction is at high temperature (600-900 ℃) strong endothermic reaction of carrying out a: CH
4+ H
2O → 3H
2+ CO, Δ H
1073=225.7kJ mol
-1, the heat energy that need to provide a large amount of is carried out in this reaction.Not 100% to produce part heat because of voltage efficiency and current efficiency when battery operated; The catalytic combustion of fuel exhaust gas is heat-flash reaction a: H
2+ 0.5O
2→ H
2O, Δ H
1073=-248.3kJ mol
-1, the caloric requirement that battery pile and tail gas catalyzed burning produce is in time removed, and prevents that localized hyperthermia impacts.For strong suction exothermic reaction, the transmission that how to promote heat is the key factor that catalyst and reactor design need consideration.
The steam reforming reaction of the fuel such as natural gas carries out on reforming catalyst in reforming reactor in other words.Reforming reactor and reforming catalyst can be placed on any fuel gas stream from the import of electricity generation system fuel gas to the solid oxidized fuel cell anode through the position.According to the difference of battery configuration and type, the place difference that the water vapour catalytic reforming reaction of natural gas arranges.Reforming reactor is placed on the outer reformation that is called on common flow chamber that battery pile outside or reforming catalyst be placed on the battery pile outside, runner.As, in US Patent No. 007320836 described cathode support tubular cells electricity generation system and US Patent No. 007326482, the described solid oxide fuel cell power generating system of US007410016, fuel reformer is placed in the battery pile outside, reforms after utilizing anode reaction tail gas to mix with fuel gas; Chinese patent (application number 200780010926.7) is placed in reforming reactor between battery pile, and reformer is the reaction tube of catalyst filling, utilizes the radiant heat of SOFC that reformer is heated; Chinese patent (application number 200810059387.2) fuel gas with water vapour after the interflow is mixed in the steam-water mixing chamber, carry together to be connected to cat reformer and to reform, connect from reformer gaseous mixture out the battery pile anode that is transported to solid oxide fuel.Reforming reactor or catalyst are placed between the common flow chamber of battery pile inside and runner, battery layers, be called inside reforming on the diffusion layer of the runner in monocell, galvanic anode.For having the Solid Oxide Fuel Cell of inside reforming ability, this Solid Oxide Fuel Cell comprises a catalyst layer that contacts with anode as Chinese patent (application number 200880107952.6).
Exhaust combustion in solid oxide fuel battery system is to flow out the fuel exhaust gas and the tail gas mixed combustion of flowing out cell cathode of anode, to comprise one as US Patent No. 7320836 and flow out the fuel exhaust gas of battery and the combustion chamber of air.Because it is higher to flow out the exhaust temperature of battery, exhaust combustion can adopt direct mixed combustion, also can adopt the combustion catalyst catalytic combustion.Catalytic combustion can make oxidation reaction reaction comparatively uniformly under the lower condition of temperature of fuel, guarantees the fuel complete oxidation.As previously mentioned, a large amount of heat is emitted in the combustion reaction meeting, can be used for preheating of air, as described in US Patent No. 7320836, or preheating of fuel and reformation, as described in Chinese patent application numbers 2011101978022.
In solid oxide fuel cell power generating system, the design of the catalytic combustion reactor of reforming reaction and tail gas need to solve following problem: (1) reforming reaction is placed on the high temperature hot-zone, carries out temperature in order to reach reforming reaction; (2) reforming reaction preferably absorbs exhaust combustion generation heat, reduces exhaust temperature, realizes that system thermal is integrated; (3) reforming reaction need to preferably have exchange heat with fuel cell reaction, in time moves away the heat that a part of cell reaction produces, and makes the Temperature Distribution of battery more even; (4) flow out the fuel exhaust gas of battery in transforming fully, in order to realize utilizing waste heat.
Summary of the invention
In the Solid Oxide Fuel Cell power station, the heat-thermal coupling of various reactions is major issues of setting up stable easily control, height integrated system structure.This patent is for the anode-supported cast solid oxide fuel cell structure Liquified gas tanker of an end sealing, for the reforming reaction of natural gas and the requirement of tail gas catalyzed combustion reaction, proposed a kind of for anode-supported cast Solid Oxide Fuel Cell, fuel rail that have fuel gas reformation and tail gas catalyzed combustion function.
A kind of fuel rail with fuel reforming and tail gas catalyzed combustion function, this fuel rail comprises the stay pipe of a both ends open, all supported catalyst layer on the inner and outer wall of stay pipe, Catalytic Layer consists of: with one or more formation porous carriers in aluminium oxide and/or cerium-based composite oxides, with at least a platinum metal element as main active ingredient, with at least a as auxiliary active ingredient in period 4 VIII family element in the periodic table of elements, contain at least a alkali metal or alkali earth metal as auxiliary agent; The weight content of platinum metal in catalyst layer is 0.01～5%; The weight content 0.5～15% of VIII family element in catalyst layer; Alkali metal or the alkali earth metal weight content 0.5～10% in catalyst layer.
This fuel rail comprises a both ends open, stay pipe fine and close, inertia, its inner and outer wall has all supported catalyst layer, the inwall catalyst layer and be in the outer wall catalyst layer of anode cavities can catalyzed aqueous vapour reformation natural gas, liquefied petroleum gas etc., produce reformed gas, supply with the generating of anode-supported cast Solid Oxide Fuel Cell; The outer wall catalyst layer that is in outside the galvanic anode chamber can catalytic fuel tail gas and air generation combustion reaction, provides heat energy to reforming reaction and the gas that flows to battery, is convenient to energy recovery.
Tail gas catalyzed burning is strong exothermal reaction, and the steam reformation of fuel is strong endothermic reaction.The present invention adopts the parietal layer catalyst loading in the surfaces externally and internally of fuel rail, and its significant advantage is as follows: the temperature that (1) is conducive to catalyst is even, improves the catalyst utilization ratio, guarantees that stable reaction carries out; (2) be conducive to strengthen the thermal coupling of the endothermic reaction and exothermic reaction, strengthening heat transfer improves the generating efficiency of system; (3) thermal coupling of cell reaction and reforming reaction improves system's generating efficiency; (4) catalysis tail gas fuel transforms fully, is conducive to waste heat recovery.
The stay pipe of fuel rail of the present invention is both ends open, inertia, fine and close high-temperature resistant tube, it can be resistant to elevated temperatures earthenware, as alumina tube, carborundum tube, corundum-mullite pipe etc., or resistant to elevated temperatures metal alloy pipe, as contain ferrous alloy and the nickel-based alloy pipe of the elements such as aluminium, zirconium, chromium.Being the passage of fuel gas in the pipe of the fine and close stay pipe of inertia, can be the single hole deferent, can be also a plurality of ducts pipes.In the present invention, it is except being the fuel air pipe, or the carrier of parietal layer catalyst.
The inner and outer wall of fuel rail of the present invention has all supported one deck catalyst, and thickness is the 5-300 micron, and the composition of parietal layer catalyst is by weight percentage: active A l
2O
320～80%, CeO
210～40%, ZrO
20～40%, La
2O
30～20%; Contain at least a of platinum metal element such as ruthenium, rhodium, palladium, osmium, iridium, platinum etc., content is 0.01～5.0%; Contain at least a of period 4 VIII in periodic table of elements family element-iron, cobalt, nickel, content is 0.5～15%; Contain at least a alkali metal or alkali earth metal as co-catalyst, its content is calculated as 0.5～10% by oxide.
Technical scheme of the present invention is as follows: stay pipe is the high-temperature resistant tube of the inertia densification of both ends open, it can be resistant to elevated temperatures earthenware, as alumina tube, carborundum tube, corundum-mullite pipe etc., or resistant to elevated temperatures metal alloy pipe, as contain ferrous alloy and the nickel-based alloy pipe of the elements such as aluminium, zirconium, chromium.The pipe internal channel of the fine and close stay pipe of inertia is the passage of fuel gas, can be the single hole deferent, can be also a plurality of ducts pipes, in the present invention it or the carrier of parietal layer catalyst.The inner and outer wall of this fuel rail all has a catalyst layer, and the parietal layer carrier material is activated alumina θ-Al
2O
3, δ-Al
2O
3, γ-Al
2O
3In a kind of and contain cerium oxide such as CeO
2, CeZrO
2, LaCeZrO
2A kind of complex carrier layer, thickness is the 5-300 micron.The preferred rhodium of platinum metal and palladium, the weight content of platinum metal in the parietal layer catalyst is 0.01～5%.Period 4 VIII family element-iron, cobalt, nickel a kind of, the weight content 0.05～10% of VIII family's element in the parietal layer catalyst.Alkali and alkaline earth metal ions element class co-catalyst preferred version is selected from least a in the elements such as IA family lithium, sodium, potassium and the IIA Ca of family, Mg, Sr, and alkali and alkaline earth metal ions oxide weight content in the parietal layer catalyst is 0.5～10%.
The parietal layer catalyst preparation process of fuel rail is as follows:
At first, the preparation of shell carrier powder.Be used for shell carrier powder and can prepare θ-Al by roastings such as aluminium hydroxides
2O
3, δ-Al
2O
3, γ-Al
2O
3Powder also can pass through θ-Al
2O
3, δ-Al
2O
3, γ-Al
2O
3The preparation of the methods such as the ball milling of carrier, the particle diameter of powder is controlled at below 5 microns.The complex rare-earth oxidate containing valuable metal such as the CeO that contain cerium
2, CeZrO
2, LaCeZrO
2Deng co-precipitation and the method for roasting preparation of powder by metal salt solution, control powder granule below 5 microns by the method for ball milling and pulverizing.
The second, the preparation of coating slurries.With alumina powder jointed, contain cerium mischmetal composite oxide powder, aluminium colloidal sol, organic binder bond, distilled water and mix according to a certain percentage, stir, make slurries.Aluminium oxide can use that θ-Al2O3, δ-Al2O3, γ-Al2O3's is a kind of.The complex rare-earth oxidate containing valuable metal that contains cerium can be used CeO
2, CeZrO
2, LaCeZrO
2A kind of.The organic binder bond that adds in slurries can increase bond strength and the thickness of coating material on tube wall, organic binder bond such as polyvinyl alcohol, methylcellulose etc., and the consumption of organic binder bond is controlled at 1～10% of slurries gross mass.The aluminium colloidal sol that contains in the slurries powder that can bond.
The 3rd, slurries form coating, preferably dip coating by the surface that the methods such as spraying, dip-coating cover the support official.The thickness of coating can change as required, is controlled between the 5-300 micron, preferably is controlled at 20～200 microns.Slurry thickness can be controlled by the concentration of slurry and obtain each time the dip-coating layer thickness, also can pass through the thickness that repeatedly dip-coating-dry run increases parietal layer.Obtain the stay pipe with the parietal layer structure after dip-coating.
The 4th, catalytic component supports.The catalyst activity component comprises platinum group metal, VIII family's element in the 4th cycle and the aforementioned various cocatalyst component of major catalyst.Supporting of they can select any surface impregnation method that is suitable for to support on the parietal layer carrier, as total immersion stain or step impregnation.When preparation catalyst of the present invention, can use the compound of the VIII family element in any decomposable platinum family compound and the 4th cycle, as halide, nitrate, oxide etc., such as rhodium chloride, palladium chloride, chloroplatinic acid, ferric nitrate, nickel nitrate, cobalt nitrate etc.VIII family's elemental constituent in platinum-group component, the 4th cycle and alkali metal and alkali figure metal promoters lithium, receive, the component such as potassium, calcium, strontium, barium can be combined with carrier with random order.Co-catalyst also can first be dispersed in the aluminium oxide slurries, also can carry out surface impregnation after forming parietal layer.Comparatively method commonly used is first to apply the carrier coating slurries on the support hanging tube, after dry and roasting, then flood alkaline-earth metal ions and roasting, final impregnating contains VIII family's elemental constituent in platinum family noble metal such as rhodium and the 4th cycle such as the solution of nickel, and drying and roasting, prepare the fuel rail that contains catalytic reforming and catalyst for catalytic combustion.
Fuel rail with fuel reforming and tail gas catalyzed combustion function of the present invention is used for the anode-supported cast Solid Oxide Fuel Cell of an end opening, an end sealing.Hydrocarbon fuel and water vapour enter distributing pipe by an end of distributing pipe, flow to fuel cell in pipe, reach the steam reformation temperature through reaching fuel gas after preheating section, issue the unboiled water steam reforming reaction in the effect of parietal layer catalyst.Simultaneously, the fuel combustion of battery is flowed out in the catalyst layer catalysis of pipe outer wall, for reforming reaction provides heat, makes the inside and outside heat of reaction coupling of stay pipe.Be placed in the distributing pipe part in tubular cells, no matter be inner wall layer catalyst and outer wall layer catalyst, the heat that all can utilize fuel cell to discharge carries out the reforming reaction of fuel.Flow out the fuel of fuel rail, electrochemical reaction occurs on battery on the one hand, can utilize on the one hand the catalyst of pipe outer wall to proceed fuel reforming reaction.Fuel mixes with the air of the battery that flows out after flowing out battery, under the effect of pipe outer wall catalyst, catalyst combustion reaction occurs.
Of the present invention have that fuel gas is reformed and the fuel rail of tail gas catalyzed combustion function, one section outside that is in battery, and its Main Function is: the preheating of fuel gas, exhaust combustion and reforming reaction, and realizing the thermal coupling of two reactions.One section is in battery, realizes the thermal coupling of reforming reaction and cell reaction.Therefore, adopt the electricity generation system of the positive electrode support solid oxygen thing fuel cell of fuel rail of the present invention, be conducive to stablize on the one hand the various piece temperature, protection system stability.Be conducive on the other hand improve the generating efficiency of system.The heat that cell reaction and tail gas fuel reaction discharge is absorbed by the fuel steam reforming reaction, can realize the generating efficiency that system is higher.Particularly the catalyst combustion reaction of a large amount of release heat and a large amount of fuel reforming reactions that absorb heats and empty preheating are integrated into the catalyst combustion reaction chamber.Adopt the electricity generation system of this fuel rail to have following three characteristics: 1) to realize the suction heat release coupling of catalyst combustion reaction and catalytic reforming reaction heat; 2) be conducive to the cooling of tail gas, prevented catalytic combustion chamber meeting excess Temperature, the system of being convenient to controls; 3) reasonably system's flow properties is convenient to the intelligent management in power station.4) avoid the high-temperature region to use rotatable parts recycled offgas and the new fuel mix that flows into, improved the reliability of whole system.
Use in order to illustrate better the distributing pipe with fuel gas reformation and tail gas catalyzed combustion function of the present invention, the present invention has provided part-structure figure, and its caption is as follows.
Description of drawings
Fig. 1. have the structure chart (A) of the fuel rail of fuel gas reformation and tail gas catalyzed combustion function, the package assembly (B) of fuel rail and anode-supported cast battery, the thermal coupling schematic diagram (C) of the fuel exhaust gas catalytic combustion on the inside and outside wall of fuel rail and reforming reaction.1. preheating section; 2. the catalyst-loaded interval of inner and outer wall; 3. preheating section (catalyst-free parietal layer); 4. react coupled section (outer wall layer catalytic combustion and inner wall layer catalytic reforming); 5. full catalytic reforming section (inside and outside parietal layer catalytic reforming); 6. air; 7. anode-supported cast battery; 8. natural gas and water vapour; 9. fuel rail; 10. the catalyst layer of outer wall; 11. the fine and close tube wall of stay pipe; 12. the catalyst layer of inwall; 13.CH
4, H
2, CO and O
214.CO
2And H
2O； 15.CH
4And H
2O； 16.CO and H
2
Embodiment
The present invention is directed to Power station structure (the Chinese patent application number 2011101978022) Liquified gas tanker of the anode-supported cast Solid Oxide Fuel Cell of an end sealing, requirement for above-mentioned fuel reforming and exhaust combustion, a kind of fuel difference pipe arrangement with fuel gas catalytic reforming and tail gas catalyzed combustion function has been proposed, mainly contain following characteristics: (1) with reforming reaction and combustion reaction be placed in respectively fuel rail inside and outside, all be in the high-temperature region; (2) thermal coupling that can be undertaken by the fuel rail wall of the catalyst combustion reaction of fuel reforming reaction and fuel exhaust gas.(3) thermal coupling of cell reaction and reforming reaction; (4) combustion reaction adopts catalyst to be conducive to tail gas completing combustion and UTILIZATION OF VESIDUAL HEAT IN.
Below by the present invention being done further detailed and concrete elaboration.
Embodiment 1
With 2000 gram alumina sols (aluminium oxide that contains 5wt%), 1500 gram distilled water, the polyvinyl alcohol of 1500 gram 20wt% is made sol solution, and sol solution stirred 2 hours under 75 ℃, made colloidal sol even.With 1500g γ-Al
2O
3Add in above-mentioned sol solution with 1500g cerium zirconium compound oxide powder, stir, then with above-mentioned mixed slurry ball milling 30 minutes, obtain γ-Al
2O
3The finely dispersed slurries of the particle of particle and cerium zirconium compound oxide.
Getting 2 external diameters and be 12 millimeters, internal diameter is 9 millimeters, and length is (pipe numbering I and II) on the alundum tube of 1.6 meters.In above-mentioned slurries dip-coating, dip-coating length is 1.5 meters with this I arm, then 120 ℃ of oven dry in lower 8 hours, 950 ℃ of lower roastings 4 hours, has obtained the complex carrier pipe I that inside and outside wall has porous carrier.In above-mentioned slurries dip-coating, dip-coating length is 1.5 meters with the II pipe, then 120 ℃ of oven dry in lower 8 hours, 950 ℃ of lower roastings 4 hours; Then in slurries dip-coating, drying and roasting once, obtained the complex carrier pipe (II) that inside and outside wall has porous carrier.
With 19.5 gram RhCl
33H
2O, 293 gram Ni (NO
3)
26H
2O, 550 gram Mg (NO
3)
26H
2The O heating for dissolving is prepared hybrid infusion solution in 1000 gram deionized waters.With the complex carrier pipe (I) that obtains previously a section of parietal layer carrier is arranged in being immersed in above-mentioned dipping solution, then take out 150C oven dry 6 hours.In order to improve the loading of catalyst, infuse and oven dry be once again for the complex carrier pipe.Then, multiple tube roasting 4 hours, has obtained to have the fuel rail (I) of catalyst layer at 650 ℃.The Electronic Speculum result shows that the thickness of inside and outside parietal layer is 24 microns, and elementary analysis shows that Catalytic Layer weight is composed as follows: Al
2O
3Be 44%, CeO
2Be 20.5%, ZrO
2Be that 18%, Rh is that 1.05%, Ni is that 7.4%, MgO is 6.5%.
With 21.6 gram RuCl
33H
2O, 253 gram Ni (NO
3)
36H
2O, 350 gram LiNO
3Heating for dissolving is prepared hybrid infusion solution in 1000 gram deionized waters.With the complex carrier pipe (II) that obtains previously a section of parietal layer carrier is arranged in being immersed in above-mentioned dipping solution, then take out 150 ℃ of oven dry, 600 ℃ of roastings 4 hours have obtained to have the fuel rail (II) of catalyst layer.The Electronic Speculum result shows that the thickness of inside and outside parietal layer is 53 microns, and elementary analysis shows that Catalytic Layer weight is composed as follows: Al
2O
3Be 45%, CeO
2Be 20%, ZrO
2Be that 19%, Ru is that 0.85%, Ni is 6.5%, Li
2O is 4.5%.
Embodiment 2
With 1500 gram alumina sols (aluminium oxide that contains 5wt%), 2000 gram distilled water, the polyvinyl alcohol of 1800 gram 20wt% is made sol solution.Sol solution stirred 2 hours under 75 ℃, made colloidal sol even.With 1500g γ-Al
2O
3Add in above-mentioned sol solution with 1500g composite La-Ce-Zr oxide powder, stir, then with above-mentioned mixed slurry ball milling 40 minutes, then add defoamer, obtain γ-Al
2O
3The finely dispersed slurries of the particle of particle and composite La-Ce-Zr oxide.
Adopt an external diameter for be 16 millimeters, to contain four internal diameters be 4 millimeters ducts, length is the upper dip-coating of the corundum-mullite pipe (III) of 1.6 meters, dip-coating length is 1.5 meters.Then 120 ℃ of oven dry in lower 8 hours, 600 ℃ of lower roastings 4 hours.Then, then dip-coating once, again 900 ℃ of roastings 4 hours, obtained the complex carrier pipe (III) that inside and outside wall has the corundum-mullite of porous carrier to support after oven dry.
With 16.8 gram Pd (NO
3) 3H
2O, 120.4 gram Ni (NO
3)
26H
2O, 118.4 gram Co (NO
3)
36H
2O, 350 gram Ca (NO
3)
26H
2The O heating for dissolving is prepared hybrid infusion solution in 1000 gram deionized waters.With the complex carrier pipe that obtains previously a section of parietal layer carrier is arranged in being immersed in above-mentioned dipping solution, then take out 150 ℃ of oven dry 6 hours.Then, multiple tube roasting 4 hours, has obtained to have the fuel rail (III) of catalyst layer at 650 ℃.The Electronic Speculum result shows that the thickness of inside and outside parietal layer is 26 microns, and elementary analysis shows that Catalytic Layer weight is composed as follows: Al
2O
3Be 43%, CeO
2Be 16%, ZrO
2Be 17.2%, La
2O
3Be that 6.2%, Pd is that 0.94%, Ni is that 3.5%, Co is that 3.6%, CaO is 3.5%.
(anode-supported cast Solid Oxide Fuel Cell is tubulose to distributing pipe as anode-supported cast Solid Oxide Fuel Cell, one end sealing, other end opening, inside is anode support, outside for cathode layer, is provided with dielectric film between anode support and cathode layer) the fuel air pipe; In use entrance point connects the common fuel chamber, and outlet passes in anode-supported cast galvanic anode chamber, and a section of distributing pipe is in the anode cavities of anode-supported cast battery, one section outside that is in anode-supported cast battery.
Be 25 millimeters with above-mentioned acquisition distributing pipe (I-III) according to shown in Figure 1 and an external diameter, 20 millimeters of internal diameters, length is 1.2 meters, and active electrode length is the anode-supported cast battery pack assembling single tube battery of an end sealing of 1 meter, and distributing pipe is placed in interior 1.1 meters of the interior length of battery cavities.The single tube battery adopts heating by electric cooker.Be 0.600 liter/min of clock with natural gas and steam according to mol ratio, the total flow of 1: 1, pass into monocell, 12 liter/mins of clocks of outside batteries blowing air, the temperature of battery is under 800 ℃, what measure battery is output current and power output under 0.8V at output voltage, the content of methane, hydrogen and the CO of mensuration from the rear outflow tail gas that burns, test result is as shown in table 1.
The gross mass content of fuel cell methane, hydrogen and carbon monoxide in output current, power and the outflow tail gas of 800 ℃ that table 1 and fuel rail fit together.
Claims (9)
1. fuel rail with fuel reforming and tail gas catalyzed combustion function is characterized in that:
This fuel rail comprises the stay pipe of a both ends open, has all supported catalyst layer on the inner and outer wall of stay pipe, and Catalytic Layer consists of: with one or more formation porous carriers in aluminium oxide and/or cerium-based composite oxides,
As main active ingredient, with at least a as auxiliary active ingredient in period 4 VIII family element in the periodic table of elements, contain at least a alkali metal or alkali earth metal as auxiliary agent with at least a platinum metal element;
The weight content of platinum metal in catalyst layer is 0.01～5%; The weight content 0.5～15% of VIII family element in catalyst layer; Alkali metal or the alkali earth metal weight content 0.5～10% in catalyst layer.
2. fuel rail according to claim 1 is characterized in that:
The platinum metal element is one or more in ruthenium, rhodium, palladium, osmium, iridium, platinum, in the periodic table of elements, period 4 VIII family element is one or more in iron, cobalt, nickel, alkali metal oxide is one or more in IA family lithium, sodium, potassium, and alkaline earth oxide is one or more in the calcium, magnesium, strontium, barium of IIA.
3. fuel rail according to claim 1 is characterized in that:
The porous carrier materials that the inner and outer wall catalyst layer of stay pipe adopts is the θ-Al in activated alumina
2O
3, δ-Al
2O
3, γ-Al
2O
3, the CeO in cerium-based composite oxides
2, CeZrO
2, LaCeZrO
2One or two or more kinds complex carrier; Catalyst layer thickness is the 5-300 micron.
4. fuel rail according to claim 3 is characterized in that:
Porous carrier materials is activated alumina θ-Al
2O
3, δ-Al
2O
3, γ-Al
2O
3In one or two or more kinds and cerium-based composite oxides CeO
2, CeZrO
2, LaCeZrO
2In the complex carrier of one or two or more kinds mixing.
5. fuel rail according to claim 4 is characterized in that:
In porous carrier materials, the weight content of each component is Al
2O
320～80%, CeO
210～40%, ZrO
20～40%, La
2O
30～20%.
6. fuel rail according to claim 1 is characterized in that:
Stay pipe is the high-temperature resistant tube of both ends open, inertia, densification, can be resistant to elevated temperatures earthenware or resistant to elevated temperatures metal alloy pipe, and this fuel rail can be single duct pipe, can be also a plurality of ducts pipe with two coaxial above ducts.
7. fuel rail according to claim 6 is characterized in that:
Resistant to elevated temperatures earthenware is alumina tube, carborundum tube or corundum-mullite pipe, and resistant to elevated temperatures metal alloy pipe is ferrous alloy or the nickel-based alloy pipe that contains one or two or more kinds element in aluminium, zirconium, chromium; The best duct of a plurality of ducts pipe is counted 2-4.
8. the application of a fuel rail claimed in claim 1 is characterized in that:
It is as the anode-supported cast Solid Oxide Fuel Cell fuel air pipe of an end sealing; In use entrance point connects the common fuel chamber, and outlet passes in anode-supported cast galvanic anode chamber, and a section of distributing pipe is in the anode cavities of anode-supported cast battery, one section outside that is in anode-supported cast battery.
9. the application of fuel rail according to claim 8 is characterized in that:
The entrance point connection common fuel chamber of this fuel rail, the port of export stretches into the anode cavities of anode-supported cast battery, inwall catalyst layer and the outer wall catalyst layer that is in the galvanic anode chamber can catalyzed aqueous vapour reformation natural gas and/or raw liquefied petroleum gas, produce reformed gas, supply with the generating of anode-supported cast Solid Oxide Fuel Cell; The outer wall catalyst layer that is in outside batteries can also catalytic fuel tail gas and air generation combustion reaction, for reforming reaction and preheating gas provide heat energy.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110413569.7A CN103165924B (en) | 2011-12-12 | 2011-12-12 | There is fuel rail and the application of fuel gas reformation and tail gas catalyzed combustion function |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110413569.7A CN103165924B (en) | 2011-12-12 | 2011-12-12 | There is fuel rail and the application of fuel gas reformation and tail gas catalyzed combustion function |
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| CN103165924A true CN103165924A (en) | 2013-06-19 |
| CN103165924B CN103165924B (en) | 2016-03-16 |
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| CN104377372A (en) * | 2014-09-05 | 2015-02-25 | 中国科学院上海应用物理研究所 | Ventilation pipe for solid oxide fuel battery/electrolysis tank, and preparation method thereof |
| CN104979575A (en) * | 2014-04-04 | 2015-10-14 | 中国科学院大连化学物理研究所 | Porous inert supporting tube type solid oxide fuel battery with two opening ends, galvanic pile and preparation method of fuel battery |
| CN108123151A (en) * | 2016-11-25 | 2018-06-05 | 中国科学院大连化学物理研究所 | Burner and application with fuel cell tail gas catalysis combustion function |
| CN108430621A (en) * | 2015-11-18 | 2018-08-21 | 埃克森美孚研究工程公司 | Heat-resisting hydrocarbon reforming catalyst based on the rhodium on θ-aluminium oxide that lanthanum is stablized |
| WO2021244599A1 (en) * | 2020-06-03 | 2021-12-09 | 潍柴动力股份有限公司 | Tail gas combustion catalyst for solid oxide fuel cell system and preparation method therefor |
| CN114618517A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Metal honeycomb combustion catalyst with integral structure, preparation method and application |
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| CN114618517A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Metal honeycomb combustion catalyst with integral structure, preparation method and application |
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| CN103165924B (en) | 2016-03-16 |
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