CN1276921A - Integrated solid oxide fuel cell and reformer - Google Patents
Integrated solid oxide fuel cell and reformer Download PDFInfo
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- CN1276921A CN1276921A CN98809740A CN98809740A CN1276921A CN 1276921 A CN1276921 A CN 1276921A CN 98809740 A CN98809740 A CN 98809740A CN 98809740 A CN98809740 A CN 98809740A CN 1276921 A CN1276921 A CN 1276921A
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Abstract
Described is an apparatus for generating electrical power. The apparatus has a plurality of tubular solid oxide fuel cells (2) contained in a reaction chamber (40). Fuel cells (2) are secured at one end thereof in a manifold block (51), the other ends thereof passing freely through apertures (63) in a baffle plate (47) to reside in a combustion chamber (41). Reaction gases are supplied to the insides of the tubular fuel cells (2) from a plenum chamber (42) below the manifold block (51) and to the reaction chamber (41) surrounding the outsides of the fuel cells through an annular inlet path, which may include a reformation catalyst. The gases inlet path to the plenum chamber (42), and the annular inlet path surrounding the reaction chamber, are both in heat conductive relation with the reaction chamber and the combustion chamber, and raise the gases to formation and reaction temperatures as appropriate.
Description
Technical field
The present invention relates to generating equipment, relate to the Solid Oxide Fuel Cell (SOFC) of this equipment specifically.
Background technology
SOFC is that the Direct Electrochemistry effect by fuel (for example hydrogen, natural gas, coal gas, or the fuel of other hydrocarbon-based) and oxidant (as air) produces galvanic equipment.SOFC includes conduct oxygen ions electrolyte (existing is base with stable zirconia), is used for air electrode (negative electrode) and fuel electrode (anode) are separated.Fuel is in anodic oxidation, and electronics is absorbed by negative electrode after being discharged into external circuit.Cathode reaction makes oxidant gas be reduced into oxonium ion, and the electrolyte of passing the energy conduct oxygen ions then is to anode.The motion of electronics in external circuit produces electric power (being typically 1 volt of 1 monocell).After loading on the battery, just produce electric current, thereby produce current density.Its value depends on the design of battery and used material.Battery is usually 700～1000 ℃ of operations down." ceramic fuel cell science and technology " described the fundamental reaction of SOFC in (author: N.Q.Minh and T.Takahashi, Amsterdam Elsevier publishing house, nineteen ninety-five), and utilizes them to produce the method for electric power.
The maximum characteristics of SOFC are transformation efficiency height (if comprising the heat utilized usually 50～90%), radiate low, used heat grade height, and integration capability height (electric power from several kW to some MW).
Utilize inner the connection or bipolar plates (generally the chromite with the doping lanthanum is a base, perhaps the high-temperature metal system), usually single SOFC is fitted together the formation battery pack system.Monocell is general to produce 1 volt of voltage, but by mode in parallel and series connection monocell is fitted together, just the voltage that can obtain wanting.Several existing structures of SOFC comprise tabular, tubulose and global design.But, it is emphasized that except above three kinds of main structures also have other design, but basic principle is identical in all designs, promptly the conduct oxygen ions electrolyte is separated fuel gas (at anode) and oxidizing gas (at negative electrode).As an example, see also article " ceramic fuel cell " (author: N.Q.Minh publishes in " U.S. pottery association journal " and rolled up 563～588 pages of the 3rd phases in 1993 76).
In order fully to realize the SOFC system, and then fully with its commercialization, it must keep reliably can not producing thermal fracture in the heating and cooling process in very long period.This system also must compare with traditional technology (for example gas turbine and diesel engine generator) has commercial competitiveness, so it must relatively cheaply be installed with being easy to.The main deficiency of existing design is to be formed by the monocell encapsulation basically.The tabular electrolyte is used in the tabular design, negative electrode and anode lay respectively at its end, the most cheap on making, but its subject matter does not apply too much stress to ceramic wafer when being seal plate, or the chemical compatibility between sealant and fuel cell.The problem of tubular design is to use seals or the sealing of open tube.In traditional tubular design, use be the manganite stay pipe of porous doping lanthanum of extruding.Electrolyte (stable zirconia) uses electrochemical vapour deposition (EVD) on stay pipe.On electrolyte, the chromite of doping lanthanum is coated in plasma spray and is used for its inner connection on the fuel cell anode with thin pulp spraying electrochemical vapour deposition (EVD).Then fuel cell is bundled into battery pack system, is packaged into the SOFC system then.Air pumps into tube interior, and tube exterior contacts with fuel gas.The one end sealing of pipe, so off-air can return from a circulation.And spent fuel also can be recycled to reclaim heat energy.
The design of tubulose is very successful, but this design can not be carried out fast thermal cycle, because thermal stress can make fuel cell break.Although transform, the limitation of this design at present is that needs 5 hours are elevated to 1000 ℃ working temperature from room temperature.United States Patent (USP) 5244752 has been described the existing generator that uses above-mentioned technology.In United States Patent (USP) 4374184,4395468,4664986,4729931 and 4751152, these SOFC have been done bigger reformation.Above-mentioned making costliness can not be made compact apparatus (10kW is following).The manufacturer of said system reduces manufacturing cost by reducing raw-material cost.For example, 90% of fuel cell weight is on the chromite air electrode of doping lanthanum, like this by using cheap raw material (high impurity content) to reduce cost greatly.Described in article " Solid Oxide Fuel Cell progress " (ECS compiles, New Jersey, 37-50 page or leaf in 1997 for author: S.C.Singhal, " Solid Oxide Fuel Cell " the 5th volume).But this cost of this system is inapplicable for small-scale production.
In order to overcome the problem of high production cost, used the thin-walled stabilizing zirconia pipe of extruding, referring to Australian Patent 675122.The internal electrode of this design is a fuel electrode, and outer electrode is air electrode (a normally lanthanum chromite).In this design, tube supports can be from wherein discharging by a passage waste gas in a heat insulation container.Be mixed with for example stabilizing zirconia of polyvinyl butyral resin and cyclohexane owing to used extrusion technique to push to make, this design has reduced the pipe cost.Above-mentioned pipe is lined up array and is contained in the heat insulation container, discharges combustion product by a passage.Directly infeed gas from the top of pipe.When forcing air to enter, combustion product is discharged from same passage.Though this design is simple, fuel cell can not move in reactor, and this equally also produces stress accumulation in fuel cell, thereby causes fuel cell to damage.
Fuel reforming to the SOFC generator in above-mentioned design also is impossible.To the reformation of fuel (in the case normally hydrocarbon fuels) is to produce carbon monoxide and hydrogen fuel and water and/or carbon dioxide mix.The fuel of this reformation is directly used in the SOFC system.In most of the cases, the reformation of this fuel is carried out in SOFC generator outside, and this just need also make whole system become huge as the valuable equipment of heat exchanger and pump and so on.Owing to lost system's lot of energy (heat) and caused the reduction of whole system efficient and the increase of complexity, above-mentioned reforming reaction of carrying out in the generator outside does not wish to occur, this has obtained partly changing in United States Patent (USP) 47299331, and wherein reformable gaseous fuel has obtained reformation in the SOFC generator.In this system, the part spent fuel is divided into two strands: one and off-air form waste gas, are partly discharged; A part of in addition waste gas then mixes with another strand spent fuel.This strand mixed gas flow mixes with reformable gaseous fuel again.Integral body has been used heat balance so that thermal loss is reduced to bottom line in this invention.Use the design of traditional tubular SOFC system in this invention, seen also above-mentioned United States Patent (USP).But this patent does not overcome original problem, as the ability of the complexity of system, price height, Fast Heating and heat of cooling circulation.This system and also very complicated.
Another design is referring to United States Patent (USP) 3377703.Here, several electrolytic tubes stand upright on the base of ceramic.Gas is by electrolytic tube and in its top burning, and hot gas flows through the heat exchanger of system then.Although this simplicity of design needs a large amount of resistant to elevated temperatures sealings, and can not bear thermal stress, and thermal stress appears at initial period faster.
Summary of the invention
Therefore the purpose of this invention is to provide a kind of generating equipment that has solid fuel cell, overcoming above-mentioned weak point, or be at least masses a kind of useful selection is provided.
At first, the present invention relates to a kind of generating equipment, comprising:
A plurality of tubular solid-oxide fuel batteries in a reative cell, each above-mentioned fuel cell all has one towards the reaction surface of inside with towards the reaction surface of outside, electrode is connected on above-mentioned each surface, and an end of above-mentioned fuel cell is installed on the seat that confluxes;
The first gas admission passage provides first gas for above-mentioned reative cell, and above-mentioned first gas stream is through the outside of above-mentioned fuel cell;
The second gas admission passage provides second gas for the stiff end of above-mentioned fuel cell, and above-mentioned second gas stream is through the inside of above-mentioned fuel cell;
From the passing away of above-mentioned reative cell combustion gas, be positioned near the end of above-mentioned fuel cell and away from the above-mentioned seat that confluxes, it allow waste gas flow out and the gas of dilution can with another gas combustion;
The electric energy aggregating apparatus, it is connected to the inside and outside of above-mentioned fuel cell to conductor;
Be reformable fuel gas one of in above-mentioned first and second gases, another kind is an oxidizing gas.According to the arrangement situation on above-mentioned fuel cell reaction surface, the passage of above-mentioned gas is used for carrying a kind of of above-mentioned reformable gas and oxidizing gas;
Above-mentioned reformable gas passage contains reforming catalyst, and is contained in the heat exchanger that is associated with above-mentioned exhaust steam passage and above-mentioned reative cell, and like this, when steady operation, gas wherein can be elevated to uniform temperature, makes gas reforming under the effect of catalyst;
Above-mentioned oxidizing gas passage is contained in the heat exchanger that is associated with above-mentioned exhaust steam passage and above-mentioned reative cell, and like this, when steady operation, gas can be elevated to reaction temperature in fuel cell, operation of fuel cells under this temperature.
The external diameter of each above-mentioned tubular fuel cell is 3～10mm, wall thickness 0.3～1mm.
Different gas flow restraint devices can be installed in the admission passage of above-mentioned oxidizing gas, flow to the oxidizing gas of above-mentioned fuel cell and above-mentioned combustion zone, thereby control ignition temperature with restriction.
The second gas admission passage can partly comprise cylindric or cone shape chamber, above-mentioned waste gas passing away can partly be cylindrical or conical equally also, it is concentric with above-mentioned admission passage, the two by the interlayer of usually making by aluminium oxide or mullite material separately, the material of above-mentioned interlayer also can be made by the material that resistive properties is lower than above-mentioned two kinds of materials.
First gas admission passage at least a portion is a cylindrical channel, is separated by interlayer with above-mentioned oxidizing gas admission passage, and above-mentioned interlayer is made by aluminium oxide or mullite, perhaps also can be made by the material that resistive properties is lower than above-mentioned two kinds of materials.
Between above-mentioned reative cell and above-mentioned waste gas passing away, one deck dividing plate is set, the hole that above-mentioned tubular fuel cell passes aforementioned barriers extend into above-mentioned exhaust steam passage, partial reaction gas can flow to above-mentioned exhaust steam passage from above-mentioned reative cell through the hole of aforementioned barriers, burns with the depleted gas that part flows out from above-mentioned tubular fuel cell.
Each above-mentioned tubular fuel cell can only support by being installed in the above-mentioned seat that confluxes.
Each above-mentioned fuel cell can pass a hole of aforementioned barriers, but between the edge in it and above-mentioned hole tangible gap should be arranged, flow to the part depleted gas of above-mentioned waste gas passing away from above-mentioned reative cell, by the gap between dividing plate and the above-mentioned corresponding fuel cell, can flow through above-mentioned hole.
Below the above-mentioned seat that confluxes, the first gas admission passage can comprise a plenum chamber, and the extended above-mentioned seat that confluxes of the stiff end of above-mentioned fuel cell.Above-mentioned plenum chamber is used for to above-mentioned fuel cell stiff end dispensing above-mentioned gas.
First gas can be oxidizing gas, and the electric power aggregating apparatus links to each other with the inside and outside electrode that is positioned at above-mentioned plenum chamber of above-mentioned fuel cell.
The first gas admission passage can comprise the gas conduit of heat conduction, and it passes the above-mentioned seat that confluxes and extends to above-mentioned plenum chamber.First length of conduit under the condition of steady operation, absorbs heat by above-mentioned reative cell from the gas of above-mentioned reative cell.
Second length to the small part of the gas conduit of above-mentioned heat conduction is passed above-mentioned waste gas passing away.
The chamber that a ring-type can be arranged is around above-mentioned reative cell, and it has the gas access to plant, flows to above-mentioned annular chamber by its gas; Also have the gas bleeder, it be positioned on the above-mentioned annular chamber with above-mentioned access to plant away from an end, make gas flow into above-mentioned reative cell from above-mentioned annular chamber.The position of above-mentioned gas bleeder is near the above-mentioned seat that confluxes.The interlayer of above-mentioned reative cell and above-mentioned annular chamber is heat conduction, for example makes by aluminium oxide or mullite, or the similar material of other thermal resistance.
One or more devices that mix mouthful and produce suction should be housed on the interlayer between above-mentioned annular chamber and the above-mentioned reative cell.Above-mentioned mixing mouth between above-mentioned two Room away from an end of reative cell gas bleeder.The device of above-mentioned generation suction produces low-pressure area by means of the effect of flowing through annular compartment gas in the annular compartment near above-mentioned mixing mouth, enter annular compartment to force gas to flow through the mixing mouth from reative cell.The device of this generation suction can be made up of Venturi tube.
Fuel cell can be the Zirconia electrolytic of stabilized with yttrium oxide, is installed in by (for example MACOR board of Corning Glass Works's sale) in a kind of glass ceramics insulator, and the seat that confluxes is made by ferritic stainless steel.
In the combustion zone firing device should be housed,, under the situation that above-mentioned oxidizing gas participates in, light above-mentioned fuel gas to produce enough heats in the part.
Control device is used for flowing of control point burning device and above-mentioned fuel gas, and fuel gas is flowed with the speed more much higher than the needed speed of generation electric power when starting.Light above-mentioned gas stream and keep above-mentioned gas stream, reach about 800 ℃ up to the temperature of the seat that confluxes a very high speed.
For general SOFC system, reaction temperature is between 400～600 ℃, and for the standard reforming reaction of using Raney nickel, the temperature of reformation is between 600～800 ℃.
Another characteristics of the present invention are to comprise space heater in above-mentioned generating equipment, and wherein above-mentioned waste gas is used for heating space, and the electric power of above-mentioned generation is used for other purposes.
Another characteristics of the present invention are to comprise the water cartridge heater in above-mentioned generating equipment, and wherein above-mentioned waste gas is used to heat the water supply in the above-mentioned water cartridge heater, and the electric power of above-mentioned generation is used for other purposes.
It is to comprise with reference to accompanying drawing being described in detail and graphic generating equipment that the present invention also has characteristics.
For the personnel that know the technology that the present invention relates to, any change of structure, the bigger variation of embodiment reach the scope that can not depart from claim restriction of the present invention to application of the present invention.Content here and description only are in order to illustrate, not have any limitation.
The accompanying drawing summary
With reference to the following drawings the preferred embodiments of the present invention are described below:
Fig. 1 is the part according to the sectional view of the generating equipment of one embodiment of the invention;
Fig. 2 is the sectional view of fixing fuel cell according to a preferred embodiment of the invention;
Fig. 3 is according to a plurality of mounted fuel cell of one embodiment of the invention and the sectional view of attached supporting construction thereof;
Fig. 4 is the sectional view that is assembled into bundle according to a plurality of fuel cells of one embodiment of the invention;
Fig. 5 is the part according to the sectional view of the generating equipment of a preferred embodiment of the invention.
Most preferred embodiment
With reference to Fig. 1, when flowing through the charge inside of battery and air of pipe, fuel flows through it when outside, in a plurality of tubular fuel cells 2, produce electric energy.The fuel cell of this structure is known in present technique, article " the SOFC electricity generation system of making by the extruded tube of diameter 2mm " (author: K.Kendall, T.W.J.Longstaff, second European solid fuel cell forum, Sweden Luceme, on May 6th～10,1996, the 195th page) in the fuel cell described be fit closely.Fuel cell is installed on the substrate 5, forms the top of reformer chamber 7.Reforming catalyst is arranged in reformer chamber, and it changes into hydrogen-rich mixture with carbon-containing fuel.
Air enters system by porous ring 16,17, and the porous ring is installed in the outside of above-mentioned chamber.Air flows through fuel cell, in the end of fuel cell and the fuel combustion of conversion, leaves pipe then.
Air absorbs heat and reaches needed working temperature in heat exchanger, above-mentioned heat exchanger is made up of concentric pipeline 4 and 6.Portion of hot is delivered to reformer chamber 7.
Interior pipe 6 ends of heat exchanger are openings, and an end of outer tube 4 is cecums.Cecum places on the burner, thereby so fuel gas be compelled to by the space water back between the pipeline.The major part of the heat of transmitting is by interior pipe, because outer tube is adiabatic.The starting of generating equipment is closed and is controlled
System starts when room temperature, opens gas trap during starting and lights the gas that flows through pipe.This can finish by the existing firing device that is installed on the outer tube.The gas stream of this moment is 5～10 times of required normal gas stream during generating electricity.Therefore, at start-up period, a rated power is the system of 1kW, and the heat that enters system is 10～20kW.A system like this contains the stainless steel of 10kg, therefore is heated to the time of working temperature less than 1 minute.In case temperature reaches about 800 ℃ (measuring the temperature of substrate), start-up period finishes.
By adjustments of gas flow to a minimum degree with system held under this temperature, system is made as zero load.The air-flow of this moment is 10～30% of a normal airflow.In case electric current output is arranged, thereby air-flow is transferred to the full scale output current.The output of electric current can be surveyed, and for example measures the variation in magnetic field.
The control of process temperature is finished by following method: regulate that air enters what, machinery control air enters the resistance of system, encircles 16 rotating rings 17 relatively.
Above-mentioned control can design in traditional burner control system, and it also may have some additional functions.
It is reliable and low-cost using the advantage of said structure, because with respect to the demand of electric current, the gas supply of system must be adjustable continuously.Weak point is that when power demand was low, most of gas combustion had been fallen, and the efficient of system is low like this.The flow of gas is adjustable or fixing (or segmentation is fixed), depends on the application scenario.
Closing device when electric current is output as zero, the flow air feed to shut down at this moment drops to below 300 ℃ up to temperature and to stop air feed.
The problem that may occur is that voltage is too low, for example because air feed causes anodic oxidation very little.This situation must be surveyed by voltage detecting, so that Current Regulation arrives zero, gas flow arrives the shutdown level.The volume of system
The about 40cm of the external diameter of whole system (allowing 5cm is used for heat insulation), high about 80cm is equipped with 800 fuel cells, each output 1.5W power when using hydrogen.The electric energy of exportable like this 1.2kW, efficient are 45% (LHV), and wherein the temperature of Chan Shenging is more than 500 ℃, and heat can reclaim.The heat that reclaims is applied to the place that other needs the inferior grade heat, for example heating space and water.In some cases, the ability of heating space and water may be a primary and foremost purpose, and generating is second Consideration.Tubular fuel cell
Anode is a porous, because it must see through gas.It is made by nickel, is mixed with electrolyte.Electrolyte is an oxygen ion conductor, for example the zirconia of stabilized with yttrium oxide.It must be very fine and close in to stop gas composition to pass through.Negative electrode forms skin, also is porous, is made by pottery, for example the LaMnO of Can Zaing
3
The making of electrolytic tube is earlier electrolyte and binding agent and plasticizer to be blended together paste, again paste mixture is squeezed into pipe, at last sintering.
The material of anode and negative electrode is made thin pulp respectively and is coated in electrolytical internal layer and skin.The anode thin pulp applies by the method for suction, and negative electrode adopts the method that is coated with or sprays of rinsing.Sinter electrode then into.
Also can use other ion conductor, and without zirconia, the CeO of typical material as mixing
2, the calcium titanate that mixes.
Other electrode material can be used CeO for anode
2(with other catalyst metals) and other oxide ceramics conductor, for example calcium titanate.Can select LaCoO for use for negative electrode
2The electro-chemical activity of these materials is than the height of above-mentioned traditional electrode material, particularly under lower temperature.
The another kind of method of making fuel cell is at first to push and the sintered anode tubes of material; Execute the skim electrolyte on this pipe, the contact area of it and anode can increase by the suction of antianode pipe; Execute one deck cathode material sintering again behind the sintering again.
The advantage of said method is that dielectric substrate is done very thinly, has reduced internal resistance; And anode is thicker, has increased the ability that anode is reformed.Electric current compiles
Electronics enters negative electrode by binding post 14 and conductive layer, and conductive layer is positioned on the negative electrode.Binding post 14 is contained in the arrival end of tubular fuel cell, and as an example, it can be made by nickel foil.
The conductive layer (not shown) as an example, can be silver-colored line or silver paste.Certainly, can use any conductor with enough conductivity.
Binding post 14 is to be made by the thick metal forming of 0.2～0.3mm, is cut into to be about the square of 8mm * 8mm, also has the tongue piece of an about 3mm * 8mm.With a rod identical it is converted into circle, is installed on the earthenware with the tubular fuel cell diameter.On tongue piece, make a call to the anode line that an aperture is used to connect adjacent fuel cell.Tongue piece terminal preferably and the end of fuel cell on a horizontal plane, thereby avoid short circuit.
The electronics that anode produces is for example made by nickel through current collector, and current collector is intertwined mutually by multi cord and constitutes.Coiling can guarantee to electrically contact like this, but also stays the space that gas passes through.Sealing
Each fuel cell is installed on the cylinder manifold 5, and it is conductor material such as stainless steel normally, with the insulator of an annular tubular fuel cell is fixed.Should seal contact between fuel cell and the insulator and between insulator and the cylinder manifold 51.Developed a kind of manufacture craft for reaching this purpose, described below in conjunction with Fig. 2.
Fuel cell uses adhesive securement on substrate, method such as above-mentioned identical.After putting into fuel cell, bonding agent is poured suction again in the pelvic cavity into.
For increasing the contact area of bonding agent and substrate, engrave standard-sized screw thread in the above.Used bonding agent is commercial aluminium oxide, zirconia and magnesium oxide bonding agent.
The material of substrate is high-quality stainless steel, and preferably the ferrite type stainless steel because its coefficient of expansion is little, therefore is difficult for producing because the problem that coefficient of expansion mispairing brings.
Like this, fuel cell is installed on the substrate 5, thereby can mode in parallel or series connection connect in groups.
For the quantity and the reliability thereof that increase the fuel cell on the unit are, fuel cell can be tied up bunchy, as shown in Figure 4.A lot of fuel cells are round a metal bar 29, and it is as current collector.As fixing of single fuel cell, this assembly, is placed in the substrate in ceramic insulator with adhesive securement again.Tubular fuel cell is fixed on the rod with line 30.
Ceramic insulator 13 and cylinder manifold 5 are preferably selected the material close with the coefficient of expansion of fuel battery electrolyte material for use, to reduce the thermal stress in the heating and cooling process.For aforesaid fuel cell, ceramic insulator is made by glass ceramics, for example the MACOR board machinable glass ceramic of Corning Glass Works's production; And cylinder manifold is fit to by the ferritic stainless steel making, utilizes the stacking implantation technique to scribble the aluminium oxide diffusion layer above.Burner
The earthenware of little sky is housed at the top of fuel cell, and its material is an aluminium oxide.Its internal diameter should be tiny so that gas velocity is enough high, allows flame remain on the outside of pipe, and size is generally 0.5mm.
Whole system is impacted the back and is placed porous wall 24 resilients by the end at fuel cell being subjected to exterior mechanical, and the hole on the porous wall is coaxial with hole on the substrate.The position of porous wall is fixing by rod 26, and there have screw to be screwed in the substrate on the rod 26 to be fixing.In order to prevent short circuit, alumina tube 25 is housed in the hole, be fixed on the porous wall.The inboard little space of alumina tube can allow air flow through.Like this, but tubular fuel cell free wxpansion in the axial direction, but, therefore can prevent the damage that causes by mechanical shock radially mobile being restricted.Reformer chamber
The substrate that has battery and lead is installed in the pipeline, forms chamber 7, and portion can reform within it, thereby system uses the fuel mixture of reforming, as natural gas or methane and water vapour.Reformer chamber contains reforming catalyst, as the nickel fiber.Feed the reformer chamber utilization of reformable fuel mixture and the method for waste gas heat exchange and fully heat, make the fuel mixture temperature be elevated to enough the reformation, for example 800 ℃.This must guarantee that reforming catalyst is placed on the hot-zone of chamber, forms carbon deposit to prevent fuel.For reaching this purpose, catalyst 30 is placed on the porous wall 31, and porous wall 31 is installed in substrate 5 following several centimeters.In addition, catalyst also can be placed in the pipe 2, and in this case, reformable fuel mixture must reach reforming temperature before entering pipe, guarantee to reform thoroughly or can not take place in the phenomenon that tube surface forms carbon deposit.The sealing of gas and the output of electric energy
The lead that connects fuel cell anode and negative pole links to each other with the outside under the condition of electric insulation and air seal.This assembly mainly comprises a rod iron 27 that the slotted hole of several centimeter length is arranged.One from the side of rod hole of gas feeds, electric wire 18,19 straight pass through.The hole that electric wire passes PTFE (perhaps similar material) ring 20 arrives excellent bottom, lateral thrust then.The plate 28 and a becket 21 of another PTFE (perhaps similar material) also have been installed in addition.Metal is threaded on the rod iron with PTFE (perhaps similar material) plate, has played the effect of air seal like this.The control of air flows
Oxygen (air) enters system by encircling 16,17 hole, and ring 16,17 is installed on the gas compartment.The gas that flows to absorbs heat from the hot gas that flows through between interior pipe 6 and outer tube 4, and portion of hot is passed to the fuel gas of reformer chamber.
Be entering of control air, one of them ring 17 can rotate.By rotating ring 17, the air that enters system can increase or reduce.For the temperature of controlling flame and then to process control, need the supply of control air.System
The electrochemical reactor that produces electric energy is made up of a series of tubular fuel cells 2, and an end of fuel cell is installed on the substrate 5 and is electrically connected.
The act as a fuel house steward of gas of substrate 5.Because fuel cell only is that an end is fixed, and can avoid thermal stress.Substrate is installed in the end of a pipeline, contains reforming catalyst in the pipeline.The other end of pipeline links to each other with a pipe, and this pipe is reformable fuel mixture input system.Form a reformer chamber 7 like this.
Like this, fuel gas is in the internal flow of pipe, and air is in its flows outside.General gas transforms under 600～1000 ℃ temperature, thereby produces electric energy.The end that conductive electric wire on the electricity process electrode or conductive paint pass to fuel cell.Usually, fuel cell is electrically connected the employing series system in the bottom of substrate (fuel-side).Because being electrically connected of fuel cell is fuel-side at substrate, main electric lead has to pass the interlayer that contains fuel.This available lead block solves, as mentioned above.
The fuel gas that enters fuel cell by fuel cell after its conversion ratio be generally 50～90%, have the fuel of dilution like this in the end of pipe.Ambient air 8 passes ring 16 and 17 hole and enters system in the mode of convection current.By means of the burning of depleted fuel, air is compulsorily entered into system, and flows through fuel cell, has consumed partial oxygen.Like this, to the burner air supply, consume oxygen there.It is the temperature of control system that air also has an effect.Usually, in order to prevent that along temperature difference excessive on the length of fuel cell the flowing velocity of air is than mobile fast 5～10 times of fuel.
By the heat-exchange system that two pipelines of placing are with one heart formed, the heat that is produced by burner is turned back to the inlet of system.Outer tube 4 has a cecum, interior pipe 6 both ends opens.Interior pipe approximately extends to the other end of pipe from the bottom of reformer chamber.Because the effect of burning forces air to enter between reformer chamber and interior pipe.Air flows through fuel cell, has transformed partial oxygen wherein by electrochemical process.The air that this part consumes oxygen burns with the fuel gas of dilution.Because outer tube has cecum, the heat of generation can not raise, but descends along the outside of interior pipe, thereby heat is passed to interior pipe, passes to the air that enters subsequently.Another system shown in Figure 5
Fig. 5 shows another system that performance is better than said system.This embodiment provides more senior heat exchanger, its structure is that reative cell 40 and combustion chamber 41 are contained in the interlayer 48 of a high heat conduction, it by one as 46 of the annuluses of a kind of reacting gas (being fuel gas in illustrated embodiment) admission passage around.
On some details, the said equipment has a reative cell 40, it by 48 of heat conduction interlayers around, for example its material is aluminium oxide or mullite.In the lower end of reative cell is the seat 51 that confluxes, and the upper end is a porous wall 47.As the embodiment of Fig. 1, an end 62 of each fuel cell 61 is installed in the seat 51 that confluxes.Fuel cell 61 vertically passes the hole 63 on reative cell 40 and the porous wall 47.The diameter in hole 63 is bigger than the diameter of tubular fuel cell 61, thereby leaves the annular gap around each fuel cell.One end 65 of fuel cell stretches on porous wall 47 in the combustion chamber 41, forms the part passing away of waste gas.In order clearly to express the sub-fraction fuel cell that only drawn among Fig. 5.In a complete system, hundreds and thousands of fuel cells will be arranged.
The bottom of combustion chamber 41 is porous walls 47, and its peripheral side and top are the interlayer 48 of heat conduction and the top cover that conical expansion 64 forms.There is an outlet 43 combustion chamber, and gas inlet pipe road 49 is passed down through hole 50, the reative cell 40 of combustion chamber 41, porous wall and confluxes seat 51 from waste gas outlet 43.Although the waste gas outlet among Fig. 5 43 is cones of butt, for improving the heat exchange of 49 of waste gas and admission lines, it is concentric that waste gas outlet 43 and admission line 49 keep in the very long distance of needs.
The bottom margin 60 of heat conduction interlayer 48 is positioned on the seat 51 that confluxes, and forms ring-shaped step 59 there.Outer wall 57 and heat conduction interlayer 48 are concentric and keep certain distance, thereby form the annular compartment 46 around reative cell 40 and combustion chamber 41.Form sealing between the circumference of outer wall 57 and conflux seat 51 and base plate 52.As an example, outer wall 57 can be made by stainless steel.The outer wall of equipment is preferably around one deck thermal insulation layer 58.
The depleted fuel gas of circulation can also have local oxidation and reformation reaction, and this need not have water to exist in fuel gas stream.
In the embodiment of Fig. 5 of the present invention, it is contemplated that each admission passage both can be used for oxidizing gas and also can be used for fuel gas.Reforming catalyst or be positioned at the bottom of annular compartment 46 perhaps is positioned at plenum chamber 42.As will be described below, to be fuel gas 45 enter from entering the mouth in the operation of present embodiment, flows through annular compartment 46; Oxidizing gas enters from the inlet 44 of admission line 49, distributes in plenum chamber; Reforming catalyst 65 is positioned at the bottom of annular compartment 46 as shown in the figure.
During equipment work, fuel gas enters shown in arrow 71 at inlet 45.The supply of fuel gas preferably should be used conventional method to pass through the fuel metering gas pressure and be controlled by system controller.The supply of oxidizing gas enters shown in arrow 70 at the inlet 44 of admission line 49, and the supply of oxidizing gas also can be controlled by system controller, for example, provides different restrictions to admission line.In some cases, need can use a small fan to realize as an example to oxidizing gas precharge.
Fuel gas is pressed the path flow shown in the arrow 72, the top cover 64 that flows through combustion chamber 41 heat conduction reaches the annular compartment 46 around heat conduction interlayer 48, fuel gas is heated when flowing through the heat conduction interlayer, the heat conduction interlayer is heated by the hot gas in burning in the combustion chamber 41 and the reative cell 40, and reative cell 40 is by the heat release heating of fuel conversion process.
The fuel gas that enters by with by mixing and be further heated from exporting the 55 sub-fraction depleted fuel gases that flow out reative cells shown in the arrow 82.Like this, when the steady operation of equipment, fuel gas is before reaching reforming catalyst 65, and temperature is elevated to about 800 ℃.Reform when fuel gas flows through on catalyst 65.
Then, the fuel gas of reformation is by 54 entering reative cell by entering the mouth shown in the arrow 73.The fuel gas of reforming upwards flows through the outside of reative cell and fuel cell, perhaps returns annular compartment 46 by exporting 55 outflow reative cells, perhaps flows out reative cell by the gap between hole 63, porous wall 47 and the fuel cell 61.If there are the gap in 49 of hole 50 and admission lines, fuel gas also can flow into combustion chamber 41 by this gap.Whether above-mentioned gap exists the material that depends on that admission line 49 and porous wall 47 are used, and promptly whether their thermal coefficient of expansion allows to cooperate closely.
Oxidizing gas enters by the inlet 44 of arrow 70 by admission line 49, by being downward through the outlet 66 that admission line reaches its bottom shown in the arrow 74,75, entering to press behind the plenum chamber 42 shown in the arrow 76 and disperses.Plenum chamber air supply very equably enters the openend 62 of fuel cell 61.Oxidizing gas enters the openend 62 of fuel cell 61 by arrow 77, and flows through therein shown in arrow 78.
Among the embodiment shown in Figure 5, it is opposite that the anode of fuel cell and negative electrode are compared with embodiment shown in Figure 1.The inner surface of electrolytic tube forms negative electrode, and electrolytical outer surface forms anode.Oxidizing gas upwards flows in pipe, and fuel gas is centered around the outside of pipe, produces chemical potential as mentioned above between the conductive layer of the inside and outside both sides of fuel cell.Being electrically connected between these conductive layers is preferred in the bottom end 62 of fuel cell 61 at plenum chamber 42, does not have fuel gas in the plenum chamber, and hot-air is only arranged usually, is environment very desirable, that be fit to.
The oxidizing gas of dilution enters into combustion chamber 41 from the upper end 65 of fuel cell 61, and they for example form pinniform flame 81 with burning by the depleted fuel gas that flows out shown in the arrow 80 from hole 63 there.Above-mentioned burning provides extra heat heating heat conduction interlayer 64 and admission line 49, and then heating enters the fuel gas and the oxidizing gas of system.Gas after dilution and the burning is by discharging in waste gas outlet 43 slave units.
Clearly, and compare in the system among Fig. 1, consider the heat production area, the structure among Fig. 5 has very big heat exchange chance.This is because reative cell 40 and combustion chamber 41 are included in entering in the chamber 46 of fuel gas, and the admission line of oxidizing gas absorbs remaining heat at waste gas outlet 43 from waste gas.System also provides the very suitable zone in equipment that is electrically connected with fuel cell, i.e. charge of air chamber below the cylinder manifold 51.From the angle of assembling, device structure is quite simple, because outer wall 57,58 is contained in heat conduction interlayer 48,64 and cylinder manifold 51 and cooperates above the base plate 52 and with them.Very straight ceramic ring sealing enough seals above-mentioned connection.Heat conduction interlayer 48,64 is easy to be placed on the step 59 of cylinder manifold 51, and fixedly porous wall 47 on corresponding position.The cylinder manifold 51 of fuel cell 61 and admission line 49 is housed, as previously mentioned, can assembles in advance and finish.
Advantage compared with prior art
The design has overcome many problems relevant with the plane fuel cell design, because:
-in planar design, 80～90% space is used for inner the connection in the device, but from directly Say on the meaning that connects that this is to the not contribution of generation of electric energy;
-inner the connection, when using metal, it with the pottery of fuel cell than very big heat is arranged The coefficient of expansion. This will cause breaking of pottery. Therefore, must be very slow when being heated to operating temperature, At least need 6 hours, this is unpractiaca;
The problem that seals in-the planar design is difficult to solve, the starting of repetition and stop to damage close Envelope;
-need chucking power to be about 100N/cm to the restriction of sealing and contact resistance2 Required Operating temperature under, the problem that this stress brings is to produce creep;
-in order to apply chucking power, need a big framework and extra parts.
The design of novelty of the present invention has overcome above problem, and fuel cell is only at one end fixing, because of This can free wxpansion. And whole system is integrated into an one piece apparatus, and its principal character is:
The supply of-air does not need air blast or pump, but makes Air Flow by free convection;
-reach and keep required operating temperature, be by means of the burning residual fuel heat to be passed to The air that enters;
-present existing fuel cell technology needs to have in the fuel hydrogen of high concentration and seldom measures Hydrocarbon. At electrode surface, it is not high enough that these gases change into the dynamics of hydrogen, because of It is needed that this does not also reach the pre-reforming stage. In the design of the present invention, reforming catalyst is placed on In the bottom of fuel cell, reformable fuel mixture is by exhaust-gas heated in the fuel chambers.
By this way, most that is commonly referred to as to " device balance " is integrated into fuel In the battery pack, this has just reached the purpose that reduces on the whole system cost.
Claims (17)
1. generating equipment comprises:
A plurality of tubular solid-oxide fuel batteries in the reative cell, each above-mentioned battery all have an inside reaction surface and an outside reaction surface, and electrode is connected with each above-mentioned surface, and an end of above-mentioned battery is fixed in the seat that confluxes;
Supply the first gas admission passage of first gas for above-mentioned reative cell, above-mentioned first gas is along the flows outside of above-mentioned fuel cell;
Supply the second gas admission passage of second gas for above-mentioned fuel cell stiff end, above-mentioned second gas is along the internal flow of above-mentioned fuel cell;
From the passing away of above-mentioned reative cell combustion gas, the end of the close above-mentioned fuel cell of above-mentioned passing away is used for waste gas is transported to outlet port away from the above-mentioned seat that confluxes, and unreacted there gas can burn mutually;
The electric energy aggregating apparatus that links to each other with above-mentioned conductor on the outside with the inboard of above-mentioned fuel cell;
Be reformable fuel gas one of in above-mentioned first and second gases, another kind is an oxidizing gas, and according to the arrangement of the reaction surface of above-mentioned fuel cell, above-mentioned each gas passage is used for carrying a kind of of reformable gas and oxidizing gas;
The transfer passage of above-mentioned reformable gas contains reforming catalyst, above-mentioned catalyst arrangement with heat exchanger that above-mentioned exhaust steam passage and above-mentioned reative cell are associated in, like this, when steady operation, gas is elevated to uniform temperature at above-mentioned catalyst place and reforms;
Above-mentioned oxidizing gas transfer passage is arranged in the heat exchanger that is associated with above-mentioned exhaust steam passage and above-mentioned reative cell, and like this, when steady operation, gas is elevated to reaction temperature at above-mentioned fuel cell place and makes operation of fuel cells.
2. generating equipment as claimed in claim 1, it is characterized in that, one porous wall separates above-mentioned reative cell and above-mentioned waste gas passing away, the hole that above-mentioned tubular cell is passed in the above-mentioned porous wall extends to above-mentioned waste gas passing away, and the hole of above-mentioned porous wall can make the gas behind the partial reaction flow into above-mentioned waste gas passing away from above-mentioned reative cell, so as with the partial reaction that from above-mentioned tubular fuel cell, flows out after gas combustion.
3. generating equipment as claimed in claim 1 is characterized in that, each above-mentioned tubular fuel cell only has an end to be installed on the above-mentioned seat that confluxes.
4. generating equipment as claimed in claim 2, it is characterized in that, each above-mentioned tubular fuel cell only has an end to be installed on the above-mentioned seat that confluxes, each above-mentioned battery passes an above-mentioned hole of above-mentioned porous wall, and tangible gap is arranged between the edge in above-mentioned battery and above-mentioned hole, flow to the gas behind the above-mentioned partial reaction of above-mentioned waste gas passing away from above-mentioned reative cell, flow through above-mentioned hole through the edge in above-mentioned hole and the gap between above-mentioned each fuel cell.
5. generating equipment according to any one of claims 1 to 4, it is characterized in that, the above-mentioned first gas admission passage is included in the plenum chamber below the above-mentioned seat that confluxes, and the stiff end of above-mentioned fuel cell passes the above-mentioned seat that confluxes, and above-mentioned plenum chamber is distributed to above-mentioned gas the stiff end of above-mentioned fuel cell.
6. generating equipment as claimed in claim 5, it is characterized in that, above-mentioned first gas is above-mentioned oxidizing gas, and above-mentioned electric energy intercon necting device for dispatching com munication system is connected with the above-mentioned inboard of above-mentioned fuel cell and the end of above-mentioned electrode in it is arranged on above-mentioned plenum chamber in the outside.
7. generating equipment as claimed in claim 5, it is characterized in that, the first gas admission passage comprises the gas conduit of heat conduction, above-mentioned conduit passes the above-mentioned seat that confluxes and extends into above-mentioned plenum chamber, one section first length of above-mentioned conduit is passed above-mentioned reative cell, and absorbs heat under the condition of steady operation from the gas of above-mentioned reative cell.
8. generating equipment as claimed in claim 7 is characterized in that, the gas conduit of above-mentioned heat conduction has one section second length to pass the part of above-mentioned waste gas passing away at least.
9. as each described generating equipment in the claim 1 to 8, it is characterized in that, the above-mentioned second gas admission passage comprises annular compartment around above-mentioned reative cell, access to plant that gas enters into above-mentioned annular compartment and gas enter above-mentioned reative cell from above-mentioned annular compartment bleeder, above-mentioned bleeder is positioned on the above-mentioned annular compartment end away from above-mentioned access to plant, and near the above-mentioned seat that confluxes, the interlayer between above-mentioned reative cell and the above-mentioned annular compartment is heat conduction.
10. generating equipment as claimed in claim 9, it is characterized in that, on the interlayer between above-mentioned reative cell and the above-mentioned annular compartment, comprise one or more mixing mouths, above-mentioned mixing mouth is communicated with between above-mentioned reative cell and above-mentioned annular compartment, far-end at the above-mentioned reative cell that leaves the above-mentioned gas bleeder, above-mentioned mixing mouth has the device that produces suction, when above-mentioned annular compartment flows through near the zone of above-mentioned mixing arrangement, produce low-pressure area there as gas, thereby gas is drawn in the above-mentioned annular compartment through above-mentioned mixing arrangement from above-mentioned reative cell.
11. as each described generating equipment in the claim 1 to 10, it is characterized in that, each above-mentioned fuel cell is all adorned a tubular ceramic insulator at the fixed position of its stiff end, the thermal coefficient of expansion of above-mentioned insulator and above-mentioned fuel cell close, and be bonded in the hole of the above-mentioned seat that confluxes, the above-mentioned seat that confluxes is to be made by the thermal coefficient of expansion material close with above-mentioned tubulose ceramic insulator.
12. generating equipment as claimed in claim 11 is characterized in that, the material of above-mentioned fuel cell is the Zirconia electrolytic of stabilized with yttrium oxide, and above-mentioned insulator is a kind of glass ceramic material, and the above-mentioned seat that confluxes is a ferritic stainless steel.
13., it is characterized in that in above-mentioned combustion zone, firing device being arranged as each described generating equipment in the claim 1 to 12, be used for producing enough heats in the part, when having oxidizing gas, light above-mentioned fuel gas.
14. generating equipment as claimed in claim 13, it is characterized in that, comprise system control device, be used to control above-mentioned firing device and control flowing of above-mentioned fuel gas at least, when starting, control above-mentioned fuel gas and flow with the high a lot of speed of the speed more required than generating, light said flow, and keep the very high speed of said flow, reach about 800 ℃ up to temperature at above-mentioned porous bearing place.
15. one kind comprises the space heater as each described generating equipment in the claim 1 to 14, wherein above-mentioned waste gas is used for the space heating, and the electric energy of above-mentioned generation is used for other purposes.
16. one kind as shown in fig. 1 with generating equipment described in conjunction with Figure 1.
17. one kind as shown in Figure 5 with generating equipment described in conjunction with Figure 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NZ3288597 | 1997-10-01 | ||
| NZ32885 | 1997-10-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1276921A true CN1276921A (en) | 2000-12-13 |
Family
ID=34192324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98809740A Pending CN1276921A (en) | 1997-10-01 | 1998-10-01 | Integrated solid oxide fuel cell and reformer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1276921A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303712C (en) * | 2001-07-05 | 2007-03-07 | 斯特凡·吕迪格·布吕姆 | Electrode arrangement |
| CN101253649B (en) * | 2005-08-31 | 2010-05-19 | 丰田自动车株式会社 | Fuel cell |
| US7732076B2 (en) | 2004-02-13 | 2010-06-08 | Alberta Research Council Inc. | Heating solid oxide for fuel cell stack |
| CN101485027B (en) * | 2006-07-05 | 2012-02-01 | 新日本石油株式会社 | Indirect inside reforming solid oxide fuel cell system |
| CN101803097B (en) * | 2007-07-19 | 2016-03-09 | 纳诺Cp有限责任公司 | Internal reforming solid oxide fuel cells |
| CN106487159A (en) * | 2015-12-25 | 2017-03-08 | 伍复军 | High-temperature fuel cell and the combined generating system of rotating thermal machine |
| CN108428966A (en) * | 2018-03-21 | 2018-08-21 | 浙江银轮机械股份有限公司 | A kind of push-in dynamic lithium battery cooling device |
| CN112042024A (en) * | 2018-04-26 | 2020-12-04 | 美科股份有限公司 | Gas distribution module and fuel cell system provided with same |
| CN115508715A (en) * | 2022-08-24 | 2022-12-23 | 华北电力大学 | Flat-plate type solid oxide battery partition testing device and testing method thereof |
-
1998
- 1998-10-01 CN CN98809740A patent/CN1276921A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303712C (en) * | 2001-07-05 | 2007-03-07 | 斯特凡·吕迪格·布吕姆 | Electrode arrangement |
| US7732076B2 (en) | 2004-02-13 | 2010-06-08 | Alberta Research Council Inc. | Heating solid oxide for fuel cell stack |
| CN101253649B (en) * | 2005-08-31 | 2010-05-19 | 丰田自动车株式会社 | Fuel cell |
| CN101485027B (en) * | 2006-07-05 | 2012-02-01 | 新日本石油株式会社 | Indirect inside reforming solid oxide fuel cell system |
| CN101803097B (en) * | 2007-07-19 | 2016-03-09 | 纳诺Cp有限责任公司 | Internal reforming solid oxide fuel cells |
| CN106487159A (en) * | 2015-12-25 | 2017-03-08 | 伍复军 | High-temperature fuel cell and the combined generating system of rotating thermal machine |
| CN108428966A (en) * | 2018-03-21 | 2018-08-21 | 浙江银轮机械股份有限公司 | A kind of push-in dynamic lithium battery cooling device |
| CN112042024A (en) * | 2018-04-26 | 2020-12-04 | 美科股份有限公司 | Gas distribution module and fuel cell system provided with same |
| CN112042024B (en) * | 2018-04-26 | 2023-09-12 | 美科电力有限公司 | Gas distribution module and fuel cell system provided with same |
| CN115508715A (en) * | 2022-08-24 | 2022-12-23 | 华北电力大学 | Flat-plate type solid oxide battery partition testing device and testing method thereof |
| CN115508715B (en) * | 2022-08-24 | 2023-06-23 | 华北电力大学 | Flat plate type solid oxide cell partition testing device and testing method thereof |
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