CN103165924B - There is fuel rail and the application of fuel gas reformation and tail gas catalyzed combustion function - Google Patents
There is fuel rail and the application of fuel gas reformation and tail gas catalyzed combustion function Download PDFInfo
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- CN103165924B CN103165924B CN201110413569.7A CN201110413569A CN103165924B CN 103165924 B CN103165924 B CN 103165924B CN 201110413569 A CN201110413569 A CN 201110413569A CN 103165924 B CN103165924 B CN 103165924B
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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 present invention relates to a kind of for anode-supported cast Solid Oxide Fuel Cell, there is catalytic fuel gas reform and the fuel rail and preparation method thereof of tail gas catalyzed combustion function.This fuel rail comprises the inertia stay pipe of a both ends open, and its inner and outer wall is all supported with catalyst layer, and thickness is 5-300 micron, and the composition of parietal layer catalyst is by weight percentage: Al
2o
320% ~ 70%, CeO
210% ~ 40%, ZrO
20% ~ 40%, La
2o
30-20%, containing at least one alkali metal or alkali earth metal oxide 0.5% ~ 10%, containing at least one 0.01 ~ 5.0% of platinum metal element as ruthenium, rhodium, palladium, osmium, iridium, platinum etc., containing period 4 VI in the periodic table of elements? I? the at least one 0.5-15% of I race element.The entrance point of this fuel rail connects common fuel chamber, outlet passes into anode-supported inertia galvanic anode chamber, its inner wall layer catalyst and be in outer wall layer catalyst in galvanic anode chamber can catalyzed aqueous vapour reforming natural gas, liquefied petroleum gas etc., produce reformed gas, the generating of supply anode-supported cast Solid Oxide Fuel Cell; The outer wall layer catalyst being in outside batteries can catalytic fuel tail gas and air generation combustion reaction, provides heat energy to reforming reaction and the gas that flows to battery.
Description
Technical field
The present invention relates to a kind of fuel rail and the 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 that one end is closed, it is while distribution fuel, the reformation of catalytic fuel gas, the burning of catalytic fuel cell outlet tail gas, realize the thermal coupling of reforming reaction and combustion reaction, cell reaction simultaneously, improve generating efficiency and the system total energy utilization ratio of system.
Background technology
Solid Oxide Fuel Cell (SOFC) is that a kind of soild oxide that adopts is as electrolyte membrance, by electrochemical reaction, the chemical energy of fuel is converted into efficiently, cleanly the Blast Furnace Top Gas Recovery Turbine Unit (TRT) of electric energy, its generating efficiency can reach more than 50%, cogeneration efficiency, higher than 80%, is the novel power generation device of the discharge reducing carbon dioxide.Solid Oxide Fuel Cell not only can use hydrogen fuel, and the natural gas of aboundresources and cheapness, liquefied petroleum gas, fuel oil, town gas and biogas etc. can also be adopted as fuel.
According to the core component-membrane electrode of Solid Oxide Fuel Cell or the configuration difference of monocell, Solid Oxide Fuel Cell can be divided into tubular cells, plate shaped battery and monolithic devices battery.Different according to the supporter of membrane electrode or battery, Solid Oxide Fuel Cell can be divided into electrolyte-supporting type, cathode support type and anode support type.Different battery configuration is different with the modular construction that electric power station system adopts in structure battery pile with the battery of type, and the mode of structure is also different, and the structure in battery pile and power station is also different.In various types of battery, with the technology of cathode support tubular solid oxide fuel cells technical development of Siemens-Westinghouse Electric of the U.S. and the battery technology comparative maturity of electrolyte-supported, the working temperature of the two battery is all at more than 900C.And 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 anode of solid oxide fuel cell reaction and can cause anode carbon deposit, and then the interface of break current conduction, reduce the performance of eelctro-catalyst, affect the gas transfer in electrode, reduce battery life.Therefore, in electricity generation system, the fuel such as natural gas are general is first synthesis gas through water vapour catalytic reforming, then carries out electrochemical reaction on galvanic anode.
Fuel reforming reaction is at high temperature (600-900 DEG C) strong endothermic reaction of carrying out a: CH
4+ H
2o → 3H
2+ CO, Δ H
1073=225.7kJmol
-1, this reaction is carried out needing to provide a large amount of heat energy.Time battery operated because of voltage efficiency and current efficiency be not 100% and produce a part heat; The catalytic combustion of fuel exhaust gas is heat-flash reaction a: H
2+ 0.5O
2→ H
2o, Δ H
1073=-248.3kJmol
-1, the caloric requirement that battery pile and tail gas catalyzed burning produce is removed in time, prevents that localized hyperthermia impacts.For inhaling exothermic reaction by force, how to promote that the transmission of heat is the key factor that catalyst and reactor design need to consider.
The steam reforming reaction of the fuel such as natural gas carries out in other words in reforming reactor on reforming catalyst.Reforming reactor and reforming catalyst can be placed on any fuel gas stream from the import of electricity generation system fuel gas to solid oxidized fuel cell anode through position.According to the difference of battery configuration and type, the place difference that the water vapour catalytic reforming reaction of natural gas is arranged.Reforming reactor is placed on battery pile outside or reforming catalyst and is placed on the common flow chamber of battery pile outside, runner be called outer reformation.As, in cathode support tubular cells electricity generation system described in US Patent No. 007320836 and US Patent No. 007326482, solid oxide fuel cell power generating system described in US007410016, fuel reformer is placed in battery pile outside, reforms after utilizing anode reaction tail gas to mix with fuel gas; Reforming reactor is placed between battery pile by Chinese patent (application number 200780010926.7), and reformer is the reaction tube of catalyst filling, utilizes the radiant heat of SOFC to heat reformer; Chinese patent (application number 200810059387.2) fuel gas with water vapour after steam-water mixing room mixes and collaborates, conveying is connected to cat reformer and reforms together, connects from reformer gaseous mixture out the cell stack anode being transported to solid oxide fuel.Reforming reactor or catalyst are placed in and the diffusion layer of runner between the common flow chamber of battery pile inside and runner, battery layers, in monocell, galvanic anode are called inside reforming.If Chinese patent (application number 200880107952.6) is for having the Solid Oxide Fuel Cell of inside reforming ability, this Solid Oxide Fuel Cell comprise one with the catalyst layer of positive contact.
Exhaust combustion in solid oxide fuel battery system to flow out the fuel exhaust gas of anode and the tail gas mixed combustion of flowing out cell cathode, flows out the fuel exhaust gas of battery and the combustion chamber of air as US Patent No. 7320836 comprises one.Because the exhaust temperature flowing out battery is higher, exhaust combustion can adopt direct mixed combustion, also can adopt combustion catalyst catalytic combustion.Catalytic combustion can make the oxidation reaction of fuel react comparatively uniformly under the condition that temperature is lower, ensures fuel complete oxidation.As previously mentioned, combustion reaction can release a large amount of heat, may 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 No. 2011101978022.
In solid oxide fuel cell power generating system, the design of the catalytic combustion reactor of reforming reaction and tail gas needs to solve following problem: (1) reforming reaction is placed on high temperature hot-zone, to reach reforming reaction carrying out temperature; (2) reforming reaction preferably absorbs exhaust combustion generation heat, reduces exhaust temperature, realizes system thermal integrated; (3) reforming reaction needs preferably have exchange heat with fuel cell reaction, moves away the heat that a part of cell reaction produces in time, makes the Temperature Distribution of battery more even; (4) fuel exhaust gas of battery is flowed out in transforming completely, to realize utilizing waste heat.
Summary of the invention
In Solid Oxide Fuel Cell power station, the heat-thermal coupling of various reaction is the major issue setting up stable easily control, height integrated system structure.The anode-supported cast solid oxide fuel cell structure Liquified gas tanker that this patent is closed for one end, for the reforming reaction of natural gas and the requirement of tail gas catalyzed combustion reaction, propose a kind of for anode-supported cast Solid Oxide Fuel Cell, there is fuel gas reform and the fuel rail of 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, the inner and outer wall of stay pipe is all supported with catalyst layer, Catalytic Layer consists of: formed porous carrier with one or more in aluminium oxide and/or cerium-based composite oxides, using at least one platinum metal element as main active ingredient, in the periodic table of elements in period 4 VIII element at least one as auxiliary active ingredient, containing at least one 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 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 that is fine and close, inertia, its inner and outer wall is all supported with catalyst layer, inwall catalyst layer and be in the outer wall catalyst layer of anode cavities can catalyzed aqueous vapour reforming natural gas, liquefied petroleum gas etc., produce reformed gas, the generating of supply anode-supported cast Solid Oxide Fuel Cell; Being in outer wall catalyst layer outside galvanic anode chamber can catalytic fuel tail gas and air generation combustion reaction, provides heat energy, be convenient to energy recovery to reforming reaction and the gas that flows to battery.
Tail gas catalyzed burning is strong exothermal reaction, and the steam reformation of fuel is strong endothermic reaction.The present invention adopts parietal layer catalyst loading in the surfaces externally and internally of fuel rail, and its significant advantage is as follows: (1) is conducive to the homogeneous temperature of catalyst, improves catalyst use efficiency, ensures that stable reaction is carried out; (2) be conducive to the thermal coupling strengthening the endothermic reaction and exothermic reaction, strengthening heat transfer, improve the generating efficiency of system; (3) thermal coupling of cell reaction and reforming reaction, improves systems generate electricity efficiency; (4) catalytic exhaust fuel transforms completely, 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 contained 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 single hole deferent, also can be multiple duct pipe.In the present invention, it is except being fuel air pipe, or the carrier of parietal layer catalyst.
The inner and outer wall of fuel rail of the present invention is all supported with one deck catalyst, and thickness is 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%; Containing at least one of platinum metal element as ruthenium, rhodium, palladium, osmium, iridium, platinum etc., content is 0.01 ~ 5.0%; At least one containing period 4 VIII element-iron, cobalt, nickel in the periodic table of elements, content is 0.5 ~ 15%; Containing at least one 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 contained 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 single hole deferent, also can be multiple duct pipe, 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 parietal layer carrier material is activated alumina θ-Al
2o
3, δ-Al
2o
3, γ-Al
2o
3in one and containing cerium oxide as CeO
2, CeZrO
2, LaCeZrO
2a kind of complex carrier layer, thickness is 5-300 micron.The preferred rhodium of platinum metal and palladium, the weight content of platinum metal in parietal layer catalyst is 0.01 ~ 5%.The one of period 4 VIII element-iron, cobalt, nickel, the weight content 0.05 ~ 10% of VIII element in parietal layer catalyst.Alkali and alkaline earth metal ions element class co-catalyst preferred version is selected from least one in the elements such as IA race lithium, sodium, potassium and IIA race Ca, Mg, Sr, and alkali and alkaline earth metal ions oxide weight content in parietal layer catalyst is 0.5 ~ 10%.
The parietal layer catalyst preparation process of fuel rail is as follows:
First, the preparation of shell carrier powder.θ-Al can be prepared by roastings such as aluminium hydroxides for shell carrier powder
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 method preparations such as the ball milling of carrier, the size controlling of powder is below 5 microns.Containing the complex rare-earth oxidate containing valuable metal of cerium as CeO
2, CeZrO
2, LaCeZrO
2pass through co-precipitation and the method for roasting preparation of metal salt solution Deng powder, control powder granule below 5 microns by the method for ball milling and pulverizing.
The second, the preparation of coating slurry.By alumina powder jointed, mix according to a certain percentage containing cerium mischmetal composite oxide powder, Alumina gel, organic binder bond, distilled water, stir, obtained slurries.Aluminium oxide can use the one of θ-Al2O3, δ-Al2O3, γ-Al2O3.Complex rare-earth oxidate containing valuable metal containing cerium can use CeO
2, CeZrO
2, LaCeZrO
2one.The organic binder bond added in slurries can increase the bond strength of coating material on tube wall and thickness, and organic binder bond is polyvinyl alcohol, methylcellulose etc. such as, and the consumption of organic binder bond controls in 1 ~ 10% of slurries gross mass.The Alumina gel contained in slurries can bond powder.
3rd, the surface that slurries cover support official by methods such as spraying, dip-coatings forms coating, preferably dip coating.The thickness of coating can change as required, controls, between 5-300 micron, preferably to control at 20 ~ 200 microns.Slurry thickness can control to obtain dip-coating layer thickness each time by the concentration of slurry, also can pass through the thickness that repeatedly dip-coating-dry run increases parietal layer.The stay pipe with parietal layer structure is obtained after dip-coating.
4th, catalytic component supports.Catalyst activity component comprises the platinum group metal of major catalyst, the VIII element in the 4th cycle and aforementioned various cocatalyst component.Supporting of they can select any surface impregnation method that is suitable for support on parietal layer carrier, as total immersion stain or step impregnation.When preparing catalyst of the present invention, the compound of the VIII element in any decomposable platinum group compound and the 4th cycle can be used, as halide, nitrate, oxide etc., such as rhodium chloride, palladium chloride, chloroplatinic acid, ferric nitrate, nickel nitrate, cobalt nitrate etc.Platinum-group component, the VIII elemental constituent in 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 aluminium oxide slurries, also can carry out surface impregnation after formation parietal layer.Comparatively conventional method first on support hanging tube, applies carrier coating slurry, after drying and roasting, then alkaline-earth metal ions is flooded and roasting, final impregnating contains platinum-group noble metals if rhodium and the VIII elemental constituent in the 4th cycle are as the solution of nickel, and drying and roasting, prepare the fuel rail containing catalytic reforming and catalyst for catalytic combustion.
The anode-supported cast Solid Oxide Fuel Cell that the fuel rail with fuel reforming and tail gas catalyzed combustion function of the present invention is closed for one end open, one end.Hydrocarbon fuel and water vapour enter distributing pipe by one end of distributing pipe, in pipe, flow to fuel cell, reach fuel gas and reach steam reformation temperature, issue producing water vapor reforming reaction in the effect of parietal layer catalyst after preheating section.Meanwhile, the catalyst layer catalyzes of pipe outer wall flows out the fuel combustion of battery, for reforming reaction provides heat, the heat of reaction inside and outside stay pipe is coupled.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 fuel cell all can be utilized to discharge carries out the reforming reaction of fuel.Flow out the fuel of fuel rail, on battery, electrochemical reaction occurs on the one hand, the catalyst of pipe outer wall can be utilized to proceed fuel reforming reaction on the one hand.Mix with the air of the battery flowed out after fuel flows out battery, under the effect of pipe outer wall catalyst, catalyst combustion reaction occurs.
Of the present invention have fuel gas and reform and the fuel rail of tail gas catalyzed combustion function, one section of outside being in battery, and its Main Function is: the preheating of fuel gas, exhaust combustion and reforming reaction, and realize two thermal couplings reacted.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 oxygenate fuel cell of fuel rail of the present invention, be conducive to stable various piece temperature, protection system stability on the one hand.Be conducive to the generating efficiency of raising system on the other hand.The heat of cell reaction and tail gas fuel reaction release is absorbed by 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 the fuel reforming reaction and empty preheating absorbing heat are in a large number integrated into catalyst combustion reaction chamber.The electricity generation system of this fuel rail is adopted to have following three features: 1) to achieve catalyst combustion reaction and be coupled with the suction heat release of catalytic reforming reaction heat; 2) be conducive to the cooling of tail gas, prevent catalytic combustion chamber meeting temperature too high, be convenient to Systematical control; 3) reasonably system flow properties is convenient to the intelligent management in power station.4) avoid high-temperature region use rotatable parts recycled offgas and newly flow into fuel mix, improve the reliability of whole system.
In order to illustrate the distributing pipe application with fuel gas reformation and tail gas catalyzed combustion function of the present invention better, The present invention gives part-structure figure, its caption is as follows.
Accompanying drawing explanation
Fig. 1. there is 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; The fine and close tube wall of 11. stay pipes; The catalyst layer of 12. inwalls; 13.CH
4, H
2, CO and O
2; 14.CO
2and H
2o; 15.CH
4and H
2o; 16.CO and H
2.
Embodiment
The present invention is directed to Power station structure (Chinese Patent Application No. 2011101978022) Liquified gas tanker of the anode-supported cast Solid Oxide Fuel Cell closed one end, for the requirement of above-mentioned fuel reforming and exhaust combustion, propose a kind of fuel pipe arrangement respectively with fuel gas catalytic reforming and tail gas catalyzed combustion function, mainly contain following feature: reforming reaction and combustion reaction are placed in inside and outside fuel rail by (1) respectively, are all in high-temperature region; (2) thermal coupling that can be undertaken by 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 and to burn completely and UTILIZATION OF VESIDUAL HEAT IN.
Elaboration detailed and concrete is further done below by the present invention.
Embodiment 1
By 2000 grams of alumina sols (aluminium oxide containing 5wt%), 1500 grams of distilled water, sol solution made by the polyvinyl alcohol of 1500 grams of 20wt%, and sol solution stirs 2 hours at 75 DEG C, makes colloidal sol even.By 1500g γ-Al
2o
3add in above-mentioned sol solution with 1500g cerium zirconium compound oxide powder, stir, then by above-mentioned mixed slurry ball milling 30 minutes, obtain γ-Al
2o
3the uniform slurries of Granular composite of particle and cerium zirconium compound oxide.
Get that 2 external diameters are 12 millimeters, internal diameter is 9 millimeters, length is (pipe numbering I and II) on the alundum tube of 1.6 meters.By this I arm in above-mentioned slurries dip-coating, dip-coating length is 1.5 meters, and then within 8 hours at 120 DEG C, dry, roasting 4 hours at 950 DEG C, obtains the complex carrier pipe I that inside and outside wall has porous carrier.By II pipe in above-mentioned slurries dip-coating, dip-coating length is 1.5 meters, then within 8 hours at 120 DEG C, dries, roasting 4 hours at 950 DEG C; Then in slurries dip-coating, drying and roasting once, the complex carrier pipe (II) that inside and outside wall has porous carrier is obtained.
By 19.5 grams of RhCl
33H
2o, 293 grams of Ni (NO
3)
26H
2o, 550 grams of Mg (NO
3)
26H
2o heating for dissolving, in 1000 grams of deionized waters, prepares hybrid infusion solution.The complex carrier pipe (I) obtained above there is one of parietal layer carrier section being immersed in above-mentioned dipping solution, then taking out and drying 6 hours at 150C.In order to improve the loading of catalyst, complex carrier pipe again infuse and dry once.Then, multiple tube roasting 4 hours, obtains the fuel rail (I) of catalyst layer at 650 DEG C.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 18%, Rh be 1.05%, Ni be 7.4%, MgO be 6.5%.
By 21.6 grams of RuCl
33H
2o, 253 grams of Ni (NO
3)
36H
2o, 350 grams of LiNO
3heating for dissolving, in 1000 grams of deionized waters, prepares hybrid infusion solution.Have one of parietal layer carrier section being immersed in above-mentioned dipping solution the complex carrier pipe (II) obtained above, then take out 150 DEG C of oven dry, 600 DEG C of roastings 4 hours, obtain the fuel rail (II) of catalyst layer.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 19%, Ru be 0.85%, Ni be 6.5%, Li
2o is 4.5%.
Embodiment 2
By 1500 grams of alumina sols (aluminium oxide containing 5wt%), 2000 grams of distilled water, sol solution made by the polyvinyl alcohol of 1800 grams of 20wt%.Sol solution stirs 2 hours at 75 DEG C, makes colloidal sol even.By 1500g γ-Al
2o
3add in above-mentioned sol solution with 1500g composite La-Ce-Zr oxide powder, stir, then by above-mentioned mixed slurry ball milling 40 minutes, then add defoamer, obtain γ-Al
2o
3the uniform slurries of Granular composite of particle and composite La-Ce-Zr oxide.
Adopt an external diameter for for 16 millimeters, be 4 millimeters of ducts containing four internal diameters, length is the upper dip-coating of corundum-mullite pipe (III) of 1.6 meters, and dip-coating length is 1.5 meters.Then within 8 hours at 120 DEG C, dry, roasting 4 hours at 600 DEG C.Then, then dip-coating once, again 900 DEG C of roastings 4 hours after oven dry, obtains the complex carrier pipe (III) that inside and outside wall has the corundum-mullite of porous carrier to support.
By 16.8 grams of Pd (NO
3) 3H
2o, 120.4 grams of Ni (NO
3)
26H
2o, 118.4 grams of Co (NO
3)
36H
2o, 350 grams of Ca (NO
3)
26H
2o heating for dissolving, in 1000 grams of deionized waters, prepares hybrid infusion solution.There is one of parietal layer carrier section being immersed in above-mentioned dipping solution the complex carrier pipe obtained above, then take out and dry 6 hours at 150 DEG C.Then, multiple tube roasting 4 hours, obtains the fuel rail (III) of catalyst layer at 650 DEG C.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 6.2%, Pd be 0.94%, Ni be 3.5%, Co be 3.6%, CaO be 3.5%.
Embodiment 3
As anode-supported cast Solid Oxide Fuel Cell, (anode-supported cast Solid Oxide Fuel Cell is tubulose to distributing pipe, one end is closed, other end opening, inside is anode support, outside is cathode layer, is provided with dielectric film between anode support and cathode layer) fuel air pipe; In use entrance point connects common fuel chamber, and outlet passes in anode-supported cast galvanic anode chamber, and one section of distributing pipe is in the anode cavities of anode-supported cast battery, one section of outside being in anode-supported cast battery.
By above-mentioned acquisition distributing pipe (I-III) according to being 25 millimeters with an external diameter shown in Fig. 1, internal diameter 20 millimeters, length is 1.2 meters, and active electrode length is the anode-supported cast battery pack assembling single tube battery that one end of 1 meter is closed, and distributing pipe to be placed in battery cavities in length 1.1 meters.Single tube battery adopts heating by electric cooker.By natural gas and steam according to 1: 1 mol ratio, total flow be 0.600 liter/min, pass into monocell, outside batteries blowing air 12 liters/min, the temperature of battery is at 800 DEG C, measure the output current under output voltage is 0.8V and the power output of battery, measure the content flowing out methane, hydrogen and CO tail gas after burning, test result is as shown in table 1.
The fuel cell that table 1 and fuel rail fit together is at output current, the gross mass content of methane, hydrogen and carbon monoxide in power and outflow tail gas of 800 DEG C.
Claims (9)
1. there is a fuel rail for fuel reforming and tail gas catalyzed combustion function, it is characterized in that:
This fuel rail comprises the stay pipe of a both ends open, and the inner and outer wall of stay pipe is all supported with catalyst layer, and catalyst layer consists of: formed porous carrier with one or more in aluminium oxide and/or cerium-based composite oxides,
Using at least one platinum metal element as main active ingredient, in the periodic table of elements in period 4 VIII element at least one as auxiliary active ingredient, containing at least one 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 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:
Platinum metal element is one or more in ruthenium, rhodium, palladium, osmium, iridium, platinum, in the periodic table of elements, period 4 VIII element is one or more in iron, cobalt, nickel, alkali metal oxide is one or more in IA race lithium, sodium, potassium, and alkaline earth oxide is one or more in the calcium of IIA, magnesium, strontium, barium.
3. fuel rail according to claim 1, is characterized in that:
The porous carrier materials of the inner and outer wall catalyst layer employing of stay pipe is the θ-Al in activated alumina
2o
3, δ-Al
2o
3, γ-Al
2o
3, CeO in cerium-based composite oxides
2, CeZrO
2, LaCeZrO
2one or two or more kinds complex carrier; Catalyst layer thickness is 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 one or two or more kinds mixing complex carrier.
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 both ends open, inertia, fine and close high-temperature resistant tube, is resistant to elevated temperatures earthenware or resistant to elevated temperatures metal alloy pipe, and this fuel rail is single duct pipe, or has multiple ducts pipe in more than two coaxial 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, the ferrous alloy of one or two or more kinds element or nickel-based alloy pipe in resistant to elevated temperatures metal alloy Guan Weihan aluminium, zirconium, chromium; The best duct number 2-4 of multiple ducts pipe is individual.
8. an application for fuel rail according to claim 1, is characterized in that:
Its anode-supported cast Solid Oxide Fuel Cell fuel air pipe closed as one end; In use entrance point connects common fuel chamber, and outlet passes in anode-supported cast galvanic anode chamber, and one section of distributing pipe is in the anode cavities of anode-supported cast battery, one section of outside being in anode-supported cast battery.
9. the application of fuel rail according to claim 8, is characterized in that:
The entrance point of this fuel rail connects common fuel chamber, the port of export stretches into the anode cavities of anode-supported cast battery, inwall catalyst layer and be in outer wall catalyst layer in galvanic anode chamber can catalyzed aqueous vapour reforming natural gas and/or raw liquefied petroleum gas, produce reformed gas, the generating of supply anode-supported cast Solid Oxide Fuel Cell; The outer wall catalyst layer being in outside batteries is also catalytic fuel tail gas and air generation combustion reaction, for reforming reaction and preheating gas provide heat energy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN104979575B (en) * | 2014-04-04 | 2017-09-26 | 中国科学院大连化学物理研究所 | The porous inert of both ends open supports tubular solid oxide fuel cells, pile and preparation method thereof |
| 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 |
| WO2017087188A1 (en) * | 2015-11-18 | 2017-05-26 | Exxonmobil Research And Engineering Company | Heat-resistant hydrocarbon reforming catalyst based on rhodium on a lanthanum-stabilised theta-alumina |
| 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 |
| CN111589452B (en) * | 2020-06-03 | 2023-04-18 | 潍柴动力股份有限公司 | Tail gas combustion catalyst for solid oxide fuel cell system and preparation method thereof |
| 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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| CN1464582A (en) * | 2002-06-20 | 2003-12-31 | 中国科学技术大学 | Anode support tube type solid oxide fuel battery |
| CN1729141A (en) * | 2002-12-20 | 2006-02-01 | 本田技研工业株式会社 | Platinum-alkali/alkaline-earth catalyst formulations for hydrogen generation |
| CN1922101A (en) * | 2004-02-17 | 2007-02-28 | 穆丹制造公司 | Fuel processor for distributed hydrogen production |
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| CN1464582A (en) * | 2002-06-20 | 2003-12-31 | 中国科学技术大学 | Anode support tube type solid oxide fuel battery |
| CN1729141A (en) * | 2002-12-20 | 2006-02-01 | 本田技研工业株式会社 | Platinum-alkali/alkaline-earth catalyst formulations for hydrogen generation |
| CN1922101A (en) * | 2004-02-17 | 2007-02-28 | 穆丹制造公司 | Fuel processor for distributed hydrogen production |
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