CN1875219A - Combustion method and apparatus for carrying out same - Google Patents
Combustion method and apparatus for carrying out same Download PDFInfo
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- CN1875219A CN1875219A CN200480031894.5A CN200480031894A CN1875219A CN 1875219 A CN1875219 A CN 1875219A CN 200480031894 A CN200480031894 A CN 200480031894A CN 1875219 A CN1875219 A CN 1875219A
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Abstract
The invention relates to recirculation flow combustors having a generally curved recirculation chamber and unobstructed flow along the periphery of the boundary layer of the vortex flow in this chamber, and methods of operating such combustors. Such combustors further have a border interface area of low turbulence between the vortex flow and the main flow in the combustor, in which chemical reactions take place which are highly advantageous to the combustion process, and which promote a thermal nozzle effect within the combustor. A combustor of this type may be used for burning lean and super-lean fuel and air mixtures for use in gas turbine engines, jet and rocket engines and thermal plants such as boilers, heat exchanges plants, chemical reactors, and the like. The apparatus and methods of the invention may also be operated under conditions that favor fuel reformation rather than combustion, where such a reaction is desired.
Description
The reference that crosses of related application
The application requires the United States Patent (USP) provisional application U.S.Provisional No.60/508 of proposition on October 3rd, 2003, and 405, and the United States Patent (USP) provisional application U.S.Provisional No.60/585 that proposed on July 6th, 2004,958 priority.
Technical field
The present invention relates to burner and combustion method, the fuel with Air mixing gas of being used for burning is so that produce the hot gas that is used for various uses.More particularly, the present invention relates to use the burner and the combustion method of the burner that has recirculation flow.The invention further relates to and be used for the ignition of mixed gas of air and fuel and with the apparatus and method of its burning.Such burner can be used for rare and super lean fuel and Air mixing gas, is used for gas-turbine engine, jet engine and rocket engine, and such as heat power equipments such as boilers, heat-exchange apparatus, chemical reactor etc.Apparatus and method of the present invention when needed, also can be operated under the condition that helps reformation of fuel (reformation) rather than burning.
Background technology
(following description or correlation technique, the definition of some terms that provide in should the detailed description according to the back is understood.)
In typical burner, be incorporated in the combustion space by the air and the fuel (can be also can not being pre-mixed of being pre-mixed) of air inlet burning, combustion process takes place in described combustion space.Can have recirculation flow, in this recirculation flow, the gas of burning in being attached to main combustion-gas flow once more before, in burner, be recycled.By introducing high speed, high temperature, a large amount of recirculation flow, heat energy and kinetic energy are injected in the main combustion-gas flow, thereby, except other advantage, also allow rare or very rare fuel/air mixture gaseous mixture to carry out stable burning, the discharging of reduction nuisance.
Although in a lot of combustion methods and device, exist recirculation flow,, the recirculation flow in burners in prior occurs in the combustion space, is not limited in being used in the specific space of organized motion.Consequently, burners in prior does not maximize the speed of recirculation flow, thereby there is not to be injected into the amount maximization of heat energy in the main combustion-gas flow and kinetic energy, and these factors, for the effective and stable burning of rare and very rare fuel/air mixture gaseous mixture, then be sought after.
For example, the United States Patent (USP) U.S.Patent NO.4 of Howald, 586,328 have disclosed a kind of burner that is essentially annular, and in this burner, combustion mixture is along the current path burning of toroidal helical shape basically.But the recirculation flow (burning gases) that is fed back to the air inlet zone in the combustion chamber does not have sufficiently high speed; Therefore, provide low-down energy to fresh fuel/air mixture gaseous mixture.The outlet of the periphery of annular airflow path enters in the turbine.And then, in the patent of Howald, between the air-flow of the burning gases of air draught and recirculation, introduce additional cooling blast.Thereby the condition that is used for that burning gases are injected into air draught or is injected into fuel/air mixture gaseous mixture air-flow suffers damage, and the energy that is offered the fuel/air mixture gaseous mixture by the air-flow of recirculation is very low.Its solution is to make the fuel/air mixture gaseous mixture denseer, but this is unfavorable, because this discharging that will cause higher ignition temperature, imperfect combustion and increase nuisance.
The United States Patent (USP) U.S.Patent No.3 of Kydd, 309,866 have disclosed a kind of process and device that is used for aphlogistic gas combustion, in this combustion process, produce recirculation (that is, in burner the gas of completing combustion combine) basically with fuel/air mixture gaseous mixture in entering burner.Similar with the patent of Howald, the burner that Kydd discloses does not maximize the speed of recirculation flow, thereby, cause low-level energy is offered main combustion-gas flow.As described in the patent of Howald, also be injected in the turbine along the air-flow of the periphery of annular race way.In addition, the burner in the patent of Kydd comprises the baffle plate of annular plate-like with holes, so the gas of burning can not be fed directly in the fresh fuel/air mixture gaseous mixture, thereby the gas that has damaged burning is injected into condition in the fuel mixture.The major defect here is, and is imported into (admitted) and mixes up hill and dale with fuel and AIR MIXTURES that the gas of the almost completely burning of carrying out eddying motion thoroughly mixes.
United States Patent (USP) U.S.Patent No.5 at Roquemore etc., 857, in 339, the closed-type scroll burner that has the inlet that hot gas recycles in primary air, have fuel and air intake, be used for before hot gas and primary air are joined fuel and/or air are imported to the hot gas of recirculation.Similar with other known burner, especially because the reforming process of the violent fuel that takes place in fresh fuel and Air mixing gas, the temperature of the hot gas of the recirculation that converges with fresh fuel and Air mixing gas promptly reduces.In this case, interpolation air and/or fuel can play opposite effect in the hot gas of recirculation, because before they ran into primary air, the temperature of the hot gas of recirculation was lowered.The geometry of combustion space makes the hot gas of recirculation join with the mode and the primary air that approach concurrent flow as much as possible.This means that its main purpose is when recirculation flow runs into the primary air of introducing, to arrive minimum hydraulic slip as far as possible.This geometry of the mixing of two air-flows is very disadvantageous, because, the condition of this " gentleness " when two airflow collisions, cause the energy transmission of the non-constant between air-flow, and, inhomogeneities in the temperature of primary air porch can be up to 100%, and the internal layer of the primary air of introducing may not be heated at all.The poor heating that this will cause the primary air introduced causes flame-out.Typical temperature profile (seeing Figure 19) for such burner shows, in the vortex combustor of sealing, in fact temperature at the primary air of the introducing of the porch of combustion space remains on the temperature identical with the temperature of the primary air that is supplied to burner.Consequently, along the axial direction and the radial direction of burner, ignition temperature has very big inhomogeneities, when fuel and Air mixing gas become rarer gaseous mixture, this will be converted into the unstability of very low flame, and the discharging of high CO and NOx.Should replenish and point out, it is very disadvantageous using additional air and/or fuel inlet in the path of recirculation flow, because, they can produce the inhomogeneities of velocity contour in recirculation flow, this will be converted into the increase of the inhomogeneities of the energy transmission between the primary air of the hot gas of recirculation and introducing.
At the United States Patent (USP) U.S.Patent No.6 of Burrus etc., in 295,801, burner utilizes the closed-type scroll operating principle, keeps pilot flame.This design has identical shortcoming with design described above.The major advantage of this closed-type scroll design is the stability of pilot flame.Why doing like this, is because in the prior art, if do not use additional device, can not reach the stability of main flame.Vortex velocity can not equal inlet air flow speed.By having the mouth of about 0.75 velocity coeffficient, air is supplied to the vortex zone.By having the shaping path of about 0.9 velocity coeffficient, the primary air air-flow is imported burner.For the desirable constant entropy speed of 100m/s, the speed of main air flow will become 90m/s, and vortex velocity will become 75m/s.By the pressure reduction that before air is supplied to vortex, can obtain, can increase the speed that air-flow is supplied to vortex, perhaps, pressure differential can be increased.But, should be noted that the temperature that is directed to the fluid in the vortex, should not be lower than the temperature of the gas in the vortex, that is, combustion product should be added in the vortex.Primary air stands unexpected expansion, causes speed to reduce.Usually, the turbulent property of eddy current causes speed to reduce.All of these factors taken together does not allow extra energy is offered the primary air of introducing.
Can put it briefly, in the prior art, in burner, use the principal character of enclosed vortex to be, the superficial layer of the primary air introduced is heated, this itself still good, can bring some improvement to the flame that keeps lean mixture.On the other hand, this shallow table heating is for flame holding and reduce discharging, can not cause any theatrical improvement.
In the recirculation flow burner of these prior aries, the recirculation flow of hot gas is by auxiliary air air-flow dilution (cooling), and then, the recycle gas that is cooled is sent to will heated primary air inlet (seeing Figure 20).Before it runs into once (master) air draught, fuel is added in the recycle gas of the heat of being diluted by the auxiliary air air-flow.Fuel is imported in the recycle gas of heat, for burning, cause very uneven condition, because very a spot of fuel can not mix fully with the recycle gas and the auxiliary air of very large amount.In this case, along with ensuing cooling, the reformation of fuel will be very violent and inhomogeneous.Then, fuel is lighted a fire, and the temperature of gas raises, the temperature reduction that fuel is reformed and caused but the rising of this temperature will partly be used to compensate.Air-flow is run into once (master) air draught (this air-flow is actually secondary gas flow, because gaseous mixture burns) then, and is cooled off once more.Because the hot gas of recirculation has been cooled twice (for the first time by the auxiliary air air-flow, the fuel that is imported into for the second time), the recirculation flow that is heated by fuel combustion has partly expended in the temperature loss that compensation is reformed, so, can not be heated at the porch primary air.The turbulent mixture of two air-flows because its result places one's entire reliance upon, and this turbulent mixture can not be guaranteed uniform mixing in whole volume, so, can not on entire cross section, heat primary air equably in the porch.This dependence to turbulent flow (mechanical mixture) is more unreliable, because two air-flows PARALLEL FLOW in fact.
In described in the above all burners, the temperature in the recirculation flow can not be higher than TIT (turbine inlet temperature (TIT)) (seeing Figure 21).According to trading off of NOx and CO discharging, the preferred temperature in recirculation flow is 1100-1200 ℃.In the recirculation of hot gas body, add air and/or fuel, cause the reduction of the temperature of recycle gas.This will cause two main results.At first, the discharging of CO can increase.The second, have to more combustion product is added in the air-flow of introducing, so that improve the temperature of the air-flow of introducing, this can cause the increase that fuel is reformed, thereby, reduce temperature.Therefore, in the burner of prior art, use enclosed vortex and recirculation flow, although can bring some improvement to the stability and the discharge performance of flame,, can't produce any breakthrough.
The United States Patent (USP) U.S.Patent No.5 of Anderson, 266,024 have disclosed and have utilized hot nozzle, by providing heat to air-flow, increase the kinetic energy of the oxidant stream that provides to blowtorch.
The United States Patent (USP) U.S.Patent No.1 of Ranque, 952,281 devices that disclosed a kind of phenomenon and be used to produce this phenomenon, by this, in having a vortex tube that is compressed fluid stream tangential inlet stream, transmit between the layer of the rotation of the fluid of heat in vortex tube, cause the fluid of rotation is separated into the outer flow of heat and cold inside stream, this may take from independent output.
Summary of the invention
The present invention relates to the recirculation flow burner, described burner have the recirculation chamber of general curved basically and in this recirculation chamber along the unobstructed air-flow of the periphery of the boundary layer of eddy current.This combustion chamber further has the eddy current in this combustion chamber and the boundary interface district of the low turbulent flow between the primary air, in this boundary interface district, takes place the very favorable chemical reaction of combustion process, and cause a kind of hot nozzle effect in the combustion chamber.Such burner can be used to burn rare or super rare fuel and air Mixture, is used for gas-turbine engine, jet engine and rocket engine, and such as heat power equipments such as boilers, heat-exchange apparatus, chemical reactor etc.Apparatus and method of the present invention when needed, also can be operated under the condition of reformation that helps fuel rather than burning.
In more detail, the invention provides a kind of burner, comprising: reactor; Inlet is used for primary fluid stream is imported in the described reactor; Outlet is used for heated fluid is discharged from described reactor; Described reactor and comprises between described inlet and described outlet: primary fluid stream zone, the major part of described primary fluid stream along the primary fluid stream path by this zone; Recirculation regions, the less part of described primary fluid stream is by this recirculation regions; Wherein, described recirculation regions is partly limited by a wall, described wall has with continuous basically mode curved inner surface and from extend to the reentry point near described inlet near the tapping point of described outlet in one direction, described inner surface is shaped in such a way and locatees with respect to described primary fluid stream path, promptly, in the operating process of described reactor, make that the segment fluid flow in described primary fluid stream path turns at described tapping point place to form the recirculation eddy current; And wherein, described inner surface is further characterized in that this inner surface does not have discontinuity, is not subjected to moving of disturbance so that cause the boundary layer basically along the periphery of described recirculation eddy current.And the chemical reaction by taking place in the border between the main linear flow of described recirculation eddy current in reactor and fluid or " interface " layer produces the hot nozzle effect.
The present invention further provides and make the react method of usefulness of fuel in the above in the described burner, said method comprising the steps of: the major part of described primary fluid stream is passed through along described primary fluid stream zone in path; By described recirculation regions, so that form the recirculation eddy current, described recirculation eddy current makes the part of the fluid in the described recirculation regions turn back to zone near described inlet to the less part that makes described primary fluid stream in path; The boundary layer that makes recirculated fluid does not have to flow around the described inner wall surface of described recirculation regions basically turbulently; The periphery and the described primary fluid stream of described recirculation eddy current are being crossed near in the zone of described inlet, and wherein, described ambient fluid stream has the speed higher than described primary fluid stream; Chase after along moving along the described ambient fluid stream of described intersection with the roughly the same direction of described main fluid; , basically not by mechanical mixture described ambient fluid stream is mixed with described primary fluid stream by thermal diffusion; Thereby, between described primary fluid stream and described ambient fluid stream, form boundary layer, and the fluid from described ambient fluid stream carries out the transmission of significant heat energy by the fluid of described boundary layer in described primary fluid stream zone.
By reference accompanying drawing and following description, enforcement of the present invention will become apparent.
Description of drawings
Fig. 1 roughly is illustrated in according to the interface between the air-flow of fuel and air Mixture and recirculation eddy current in the burner of the present invention.
Figure 1A roughly is illustrated in the part of the boundary layer between the air-flow of the fuel of recirculation eddy current and introducing and Air mixing gas, wherein, and symbol X representative " hot " CO molecule in the perisphere of recirculation eddy current.
Fig. 2 is a curve map, is illustrated in according in the burner of the present invention CH
4, T and CO and recirculation eddy current and fuel and air Mixture air-flow between the functional relation of time of contact.
Fig. 3 is a curve map, the emission level of expression NOx and the functional relation between the ignition temperature.
Fig. 4 is illustrated in the air-flow of fuel and air gas mixture, temperature and V
2/ V
1Ratio between functional relation.
Fig. 5 represents the functional relation of CO and CH concentration (%) and burning time.
Fig. 6 is according to the cutaway view as the burner that sprays burner of the present invention.
Fig. 7 is the phantom along arrow VII intercepting of Fig. 6.
Fig. 8 is the part schematic sectional view according to annular burner of the present invention.
Fig. 9 is the longitudinal section along another embodiment of the annular burner of the line design of Fig. 8.
Figure 10 is an embodiment of burner shown in Figure 8.
Figure 11 is the vertical schematic sectional view according to can-type chamber of the present invention.
Figure 12 is the end-view of seeing when entrance side is observed according to burner of the present invention, an embodiment of expression inlet.
Figure 13 is the another one embodiment with the similar inlet shown in Figure 12.
Figure 14 represents to be combined with the longitudinal section according to the gas-turbine unit of annular burner of the present invention.
Figure 15 represents to be combined with the longitudinal section according to the another one embodiment of the gas-turbine unit of annular burner of the present invention.
Figure 16 is the view of the arrow XVI intercepting in Figure 16.
Figure 17 is the view that the part of burner shown in Figure 15 is amplified.
Figure 18 represents the speed V of the level of carbon monoxide (CO) with respect to the recirculation eddy current
2With inlet flow velocity V
1The functional relation of different ratio.
Figure 19 represents the typical temperature profile for the closed-type scroll burner.
The Temperature Distribution of Figure 20 in the recirculation flow burner of prior art.
Figure 21 is illustrated in the Temperature Distribution of the prediction in the recirculation flow burner of prior art.
Figure 22 is illustrated in the temperature survey point in the burner lining.
The specific embodiment
Now with reference to the accompanying drawings the present invention is described in more detail, described accompanying drawing is diagrammatically represented the embodiment according to the non-limiting example of burner of the present invention.
As preliminary matter, we provide some definition, so that understand this specification and claims.
Flame is in the thin zone of the chain oxidation reaction of this place's beginning
The chain reaction of combustion fuel oxidation
Catch fire (perhaps incipient stage of chain oxidation reaction
As " by lighting a fire "
The middle igniting of using)
Aphlogistic burning takes place in the whole volume of primary air equably
The phenomenon of oxidation reaction
Reactor is realized the device of chemical reaction
In this manual, device as described herein represented in general using term " burner ", although as will be described, according to device of the present invention, can operate in the reformation that helps fuel rather than under the condition of burning.Term " reactor " is here as the alternative term of the more generality of " combustion chamber " or " combustion space ", because under some condition, fuel reformed be here the prevailing process that is taken place.
In addition, should be kept in mind that burning and/or reforming is the chemical process with complicated dynamic (dynamical) complexity, in any given reactor, in the various time thousands of kinds of different chemical reactions will take place.Usually, at the reactor concentration-response, except fuel directly is oxidized to carbon dioxide and water, also comprise comprising a lot of centres and other reaction:
A) thermal decomposition of fuel, for example,
B) partial oxidation of fuel, for example,
(,, providing methane) together with the corresponding different reaction that takes place with other fuel as the most basic example.Particularly, when temperature is lower than the temperature of burner of prior art, need not to use catalyst, these reactions will take place.In addition, we also observe (for example):
C) fuel is reformed,
D) fuel combustion,
E) fuel is reformed,
F) fuel combustion,
F) fuel combustion,
G) fuel is reformed,
Be also noted that here fuel is reformed and burning, sometimes both be characterized as one type chemical reaction, described chemical reaction is OR and oxidation reaction.This be because, under each situation, all " heat " product (H
2O and CO) all be that oxidized process forms.Of course it is to be understood that in the fuel reforming process " cold " product (CO) is also arranged, described product is reduced reaction and forms.
Now forward accompanying drawing to, Fig. 6 and 7 is two views of one embodiment of the present of invention.Present embodiment provides a kind of burner 10, this burner has combustion space or reactor 16, described reactor is importing to primary fluid stream between inlet of using in the combustion space 18 and the outlet 20 of heated fluid being discharged usefulness from the combustion space, described combustion space comprises: a primary fluid stream zone, and most of primary fluid stream flows through by this zone along the primary fluid stream path; A recirculation regions, the less part of primary fluid stream flows through by this zone along path.The race way is partly limited by a wall, described wall has along a direction with continuous basically mode curved inner surface 21, described inner surface 21 is in such a way with respect to primary fluid stream and primary fluid stream via configuration and shaping, promptly, this mode causes that fluid in the primary fluid stream path is at the recirculation eddy current of the part at tapping point place, before fluid is discharged in the combustion space, described recirculation eddy current turns back near the reentry point that enters the mouth from the tapping point near outlet, and then, described inner surface quilt basically is not subjected to the moving of disturbance so that cause boundary layer along the periphery of described recirculation eddy current without any configuration by phased manner.
Preferably, when reactor 16 plays time spent of doing of combustion chamber, the volume of recirculation regions is not less than the volume in primary fluid stream zone.But when the time spent of doing of the reformer that will describe below reactor 16 plays, the volume of recirculation regions preferably is not less than the twice of the volume in primary fluid stream zone.
As further describing, in reactor 16, the chemical reaction by in the border between the linear flow that occurs in described recirculation eddy current and main fluid or " interface " layer produces a kind of hot nozzle effect.
According to burner of the present invention, provide a kind of recirculation flow.On the fluid stream and the interface between the primary fluid stream in the primary fluid stream zone in this eddy current, be one " border " or " interface " layer.Between the wall and eddy current of recirculation regions, also have a perisphere or boundary layer, this boundary layer has laminar flow basically.In more detail, boundary layer has the turbulence level less than 0.2 (preferably between 0.008-0.01).
Undisturbed recirculation flow in perisphere and boundary layer provides following advantage:
-vortex sheet does not mix in vortex along radial direction basically, and this makes it possible to keep the scatter chart of hot gas molecule in vortex, simultaneously, mainly is CO, CO
2And H
2" heat " molecule of O moves to the periphery of recirculation flow vortex, and CO is in this place's burning, and " cold " molecule and dissociation product that fuel molecule is reformed, secondary CO, H
2, and oxygen, move at the center from the periphery to vortex, and at this place, they participate in oxidation reaction in vortex.This separation is to take place as the result that the inertia in centrifugal force field spreads.Thereby interface or joint between the primary fluid stream of recirculation eddy current and introducing will be in the highest possible temperature, and vortex always has the supply of combustible material, and without any the mixing of layer.
-because the hot nozzle effect, and since the low-down turbulence level of recirculation flow (this is to reach by the surface that a circle is provided, described circular surface is configured to guarantee that nature flows, and be made into to guarantee not to be subjected to flowing of disturbance along this surface), the inside of vortex is to the speed of its perisphere speed greater than the primary fluid stream of introducing.
The existence of-boundary layer and perisphere makes that fuel can completing combustion in about 2ms or shorter time.
-along vortex perisphere generation reforming reaction, comprise CO
2Reaction forms 2CO with C.Although when beginning forms " heat " molecule and " cold " molecule,, when this layer when entrance area joins in the primary fluid stream again, except other factors, mainly be owing to the contacting of the locular wall of heat, significantly heated.As will be described further, when mixing in the porch with fuel of introducing and Air mixing gas rightly, the peripheral eddy current of the CO of this heat, it is very favorable acting as a fuel.
Recirculation flow can change with respect to the ratio of master's (linearity) fluid stream in burner.Enter the fluid of vortex and the ratio of leaving the fluid of burner in the exit, play a part the operator scheme of combustion chamber at reactor, preferably, be not less than (7%) 7 percent, play in the operator scheme of reformer at reactor, be not less than 10 (10%).
As discussed above, in order to keep this fluid stream of desired depth, the surface of this chamber should be crooked, keeps it along a direction bending (for example, not crooked to and fro) in continuous basically mode.When the fluid in the exit has about 1100 ℃ temperature, the degree of depth of this boundary layer is about 1mm, when fluid in the temperature of outlet when being about 800 ℃, this degree of depth is about 2mm, in lower temperature, this degree of depth is firmly got many, for example, in the time of 380-420 ℃, low always will have the degree of depth greater than the diameter of the centronucleus of the recirculated fluid in the recirculation eddy current to this boundary layer.
Thereby, in the periphery of vortex runs into the joint or the zone near inlet of the primary fluid stream that is directed to the introducing in the combustion space, obtain following condition: the highest temperature is located on the interface of two fluid streams, and, between flowing, two fluids of following the joint motion on the same direction have higher relative velocity.The result of these two conditions is, to the interfacial very strong heat transmission of the primary fluid stream of introducing, this heat transmission is characterised in that from the periphery of vortex, because condition recited above, the speed that heat is transmitted is very high.Thereby vortex can be with the boundary layer transferring heat energy of effective and efficient manner to the primary fluid stream of introducing.Therefore, the superficial layer of the primary fluid stream of introducing is lighted a fire, and burn steadily, and it is irrelevant with the fuel/air mixture ratio, play a part pilot flame, but, between two fluids stream, do not have tangible turbulent mixture, this Turbulence Mixed credit union cause the homogenizing of formation, temperature of high spot and " cold " point and other existing closed-type scroll burner intrinsic unwelcome phenomenon.Should be noted that result, at first as the inertia diffusion, burnt fuel arrives the superficial layer of the fluid stream of introducing, the direction of " cold " leaves for the core of vortex, thereby the condition of chain reaction is provided, promptly, condition with the speed oxidation suitable with the speed of burning, and along with the further increase with respect to the speed of the air-flow of introducing of the speed of vortex, the speed of burning also can increase, thereby, utilize much rare gaseous mixture (k than what use in traditional burner
eAbout 0.5) causes controlled explosive combustion.This phenomenon causes the increasing suddenly of temperature of the air-flow introduced, and, as its result, cause just in the close porch of burning, rapidly with the entire body that heats the air-flow of introducing equably, thereby, the kinetic energy of the air-flow of introducing or speed begin to increase from entrance area, and this increase continues up to exit region, and therefore the hot nozzle effect is provided, this hot nozzle effect recycles eddy current with momentum, makes it with higher speed motion.It should be noted that, need not vortex institute recirculation flow mixes with the machinery (turbulent flow) of the fluid stream of introducing, only go up mechanism that face mould describes this heating rapidly by the air-flow introduced takes place, do not exist the vortex recirculation flow to mix with the machinery (turbulent flow) that the fluid of introducing flows by utilizing.
In burner according to the present invention, utilize the hot nozzle phenomenon, make it possible to increase fluid flow and cross the speed that the combustion space is left in outlet, meanwhile, almost completely eliminated recirculation (vortex) stream and the turbulent mixture that flows main body by the fluid of combustion space.Thereby reduce the loss in the combustion space significantly.In order to produce the hot nozzle effect, adopt circular surface, and this circular surface is without any fluid flow disturbance element, opening for example, groove, projection, fluid intake etc., especially, by inertia above-mentioned diffusion and the main body by the fluid stream introduced rapidly heating combine with high-temperature interface between two fluids stream, guaranteed to recycle the redistribution of the medium gas molecule of eddy current.There is not the mixing of the formation that will cause high spot and " cold " point, guarantees minimum NO
xThe formation level.Because combustion product is not mixed with the fluid of introducing by turbulent flow (mechanical mixture), so, can be the fuel and the Air mixing gas of very rare introducing, it is rarer can not become, because burning gases and fuel/air mixture gaseous mixture move (in identical direction with different speed) in the mode of concurrent flow, there is not mechanical mixture between them.This advantage make it possible in theory can oxidation at any hydrocarbon fuels temperature, the burning that keeps very rare gaseous mixture.
The ignition temperature of hydrocarbon fuels can be lower than 500 ℃, and the Outlet Gas Temperature of burner is low to 350-330 ℃.This is an oxidizing temperature, so, if use traditional burner structure, then CO
2And H
2The formation speed of O will reduce above 1000 times.But, since inertia above-mentioned diffusion, new CO, the CO that forms
2And H
2O in zone with higher fuel content (to the periphery) from the center of vortex, reach then speed to the layout again of boundary layer, than high several times of the burning velocity of about 1m/s of standard, and the oxidation rate of the propellant composition in burner according to the present invention is the same order of magnitude with burning velocity in the burner in prior art.
As described above, there is not fluid (comprising fuel) to add in the combustion product in the recirculation flow (not adding at least in the lip-deep major part of circular recirculation flow between the entrance and exit of combustion space) to, the turbulence level of recirculation flow non-low (below the minimum value of any traditional burner).Consequently, in vortex, there is not carbon particulate to form.Its favourable result is, do not exist from the thermal radiation loss of recirculation flow to burner wall, and at recirculation flow in the zone that the separation of leaving burner and separating to the combustion product that entrance area flows is lighted, the lower temperature of burner wall.Should be noted that temperature in the burner wall of this burble point upstream, to the CO level without any influence.
To vortex surface and the fuel of chemical reaction and the heat exchange between the air Mixture, not only determine by the temperature field; It depends on the chemical composition of vortex and fuel and air Mixture.Between the temperature of two air-flows, there are differences (the vortex temperature is higher), and there are differences between their chemical composition that (vortex includes more CO
2And H
2O, fresh gaseous mixture comprises more fuel and oxygen).Thereby, if two air-flows do not have mechanical mixture in same direction motion, produce the condition that is used for diffusion process, more particularly, produce the condition that is used for thermal diffusion and concentration diffusion.The air pressure diffusion can be ignored, and it is being important when controlled explosive combustion changes only.
In the operation process of burner, the ratio of thermal diffusion and concentration diffusion changes; But concentration is diffused in the heat exchange between vortex and the fuel-air mixture always preponderates.In fact the concentration diffusion has conclusive effect for the intensity of heat exchanging process.If the inclusive words of chemical reaction, be to be difficult to accurately to evaluate concentration gradient in the middle of heat exchanging process.Should be noted that CH in the boundary layer in eddy current and fuel and air stream
4(or other fuel) and O
2The variation of concentration, not only influence the thermal energy transfer process, and influence the Direction of Reaction (directly reaction and back reaction).For example, if in fuel and air Mixture CH
4Concentration increase (because and the set-point of design compare the result of coefficient of equivalence increase), in boundary layer, the fuel reforming process will begin to occupy advantage.Combine with the oxygen ratio to the vortex supply, this will cause the temperature of vortex periphery to descend, and consequently, the temperature that arrives the molecule of vortex center part also can reduce.Simultaneous two processes will cause the vortex temperature to be reduced to below the subcritical value, cause flame-out.Here it is why as doing in the past the simple mechanical mixture by eddy current and fuel and Air mixing gas can not solve the reason of the stable burning of lean mixture because, in this case, provide heat energy to fuel and air Mixture, be accompanied by CO
2And H
2Increase when O supplies with, reduce the temperature of vortex and fuel and air Mixture simultaneously.According to the present invention, diffusion process is preponderated between two air-flows (not having mechanical mixture between them), and for the speed of thermal energy consumption person-fuel and air Mixture, the heat energy energy of the porch of meet at air-flow (vortex) has the speed of increase.
Strong vortex starts the hot nozzle effect in such a way to the heat transmission of fuel/air mixture gaseous mixture.The perisphere of fuel and air Mixture air-flow always with very high heat transfer rate from vortex periphery and CO
2, CO and H
2" heat " molecule of O is accepted heat energy.Therefore, provide the fight condition of the burning of keeping this layer of the peripheral point of fuel and air stream.In case this perisphere is lighted a fire, burning is just propagated the main body that spreads all over whole fuel and air draught with very high speed, and air velocity begins to raise under the effect of hot nozzle effect.Consequently, the kinetic energy of fuel and air draught increases.The stable burning (retention flame) of fuel and air draught perisphere not only by the high temperature of eddy current and from the vortex periphery the high-speed heat transmission to the periphery of fuel and air guarantee that wherein, described high-speed heat transmission forms a kind of " pilot flame ".And, CO
2, CO and H
2The O molecule makes under any instantaneous state to continuous and supply abundance of this " pilot flame " layer, for the fuel-air ratio of minimum, and under the situation that the supply of fuel is fluctuateed suddenly, guarantees the flame that continues.
Fuel and oxygen molecule with move along opposite direction from " heat " molecule that vortex moves to fuel and air Mixture by diffusion.This is the concentration diffusion.Nitrogen molecular spreads (thermal diffusion) with very little amount from vortex to fuel and air Mixture, nitrogen can not move in vortex from fuel and air Mixture mostly, because the concentration of the nitrogen in vortex and fuel and air Mixture equates basically.Enter the part of the fuel in the boundary layer between eddy current and fuel and the air draught, lighted a fire, still, the main bulk of fuel in this layer is reformed.Once (" heat ") CO molecule, and the part of hydrogen rests in the boundary layer.
The molecule of some stop is oxidized to CO
2And H
2O, they turn back in fuel and the air Mixture.Most once (" heat ") CO molecule and hydrogen is with CO and H
2Form turn back in fuel and the Air mixing gas.They produce " impact " of vortex." cold " molecule (obtaining) as the result who reforms, so-called secondary CO, H
2And oxygen, will move to the center (they have lower inertia, because its heat movement speed is lower) of vortex.They can not all arrive the center.Part in them in the road that move at the center, will be oxidized to CO at it
2And H
2O is turned back to the periphery (being spread by inertia) of vortex by centrifugal force, or the like.
This process is diagrammatically shown among Fig. 1 and Figure 1A, wherein, and some representative " heat " CO, CO
2, H
2O and H
2Molecule, plus sige representative " cold " fuel molecule and oxygen.Arrow is represented the direction of motion of aforesaid molecule, and the point that the fuel of recirculation eddy current and introducing and the air-flow of air Mixture meet is illustrated in " O " and locates.
The partial view of the signal of the amplification of the boundary layer of the fuel of recirculation eddy current and introducing and the air-flow of air Mixture is illustrated among Figure 1A.Symbol " X " representative is by the CO in the perisphere that form, that be input to vortex of reforming.The figure shows at entrance area and be diffused into the fuel of introducing and the CO in the air Mixture, greatly help burning.As will be appreciated, although the speed V2 of recirculation eddy current is greater than the fuel of introducing and the speed V1 of air Mixture, but, the speed V3 of recirculation eddy current perisphere is far below the speed of fuel of introducing and air Mixture air-flow (velocity gradient is arranged from the surface, and the average speed in this layer is greatly in 1/5 the scope of V1).
The process that takes place in boundary layer is shown in the chart of Fig. 2.As can be seen, As time goes on, fuel level (CH
4) descend, still, temperature (T) almost remains unchanged (do not increase, and in traditional burner, then can increase), because the reformation of strong fuel is being carried out always, forms " cold " and " heat " CO molecule simultaneously.Time of contact approximately through 2/3 after, perhaps, in the present embodiment, approximately through 0.7 to 0.8ms, temperature T begins to rise after two air-flows meet.
Enforcement is to make the design of burner meet following dimensional configurations relation according to the usually preferred mode of combustion method of the present invention:
a≥1.4b
d≤2.2b
2r+b≥c≥r+b
Wherein:
R is the radius (see figure 6) of circular surface;
A is the inlet of combustion space and the distance between the outlet;
B is the height of inlet portion;
C is the full-size of combustion space in the radius r direction;
D is the height of export department.
If d is greater than 2.2b, the cross-sectional area of hot nozzle can be too big, can not reach the required fuel that gives the initial momentum of vortex and the speed of air draught.If c is greater than 2r+b, cross-sectional area is too big, can not reach the speed of required fuel and air draught, and it will reduce for the effect of vortex, and the speed of vortex in the zone at the interface of itself and fuel and air draught can be too low.Preferably, the cross-sectional area of outlet is not more than 2.2 times of cross-sectional area of inlet.For the entrance cross-section area that plays a part at reactor to use in the operator scheme of combustion chamber, when needs changed to reactor and play a part the operator scheme of reformer, the area of entrance cross-section reduced.
The time of contact of size a decision vortex and fuel and air draught.Preferably, this time should be greater than 1ms.According to the entrance velocity of fluid in the porch, can obtain size a, described entrance velocity is preferably 10 to 20m/s.
When fresh fuel and air Mixture are heated (rising of temperature is about 150 ℃), in fuel and air draught, exist uneven temperature distribution history usually, in traditional burner, usually before igniting, during the hot gas heating that is recycled when gaseous mixture, the heating of this fresh fuel and gaseous mixture takes place.The inhomogeneities of temperature can this means that the injection stream of each air-flow (jet of flow) in fact can remain on and the identical temperature of temperature that enters burner air draught before up to 100%.At the end of fuel combustion, the inhomogeneities of temperature is roughly the same.If the outlet temperature of burner should be about 1200 ℃, because inhomogeneities above-mentioned, temperature can be up to 1500 ℃ in air-flow.Although NO in the time of 1200 ℃
2Level be acceptable, but at high temperature the discharging of nitrous oxide is significantly higher.This is illustrated among Fig. 3, and wherein, curve I represents the discharging for the nitrous oxide of hotter fuel-air mixture layer, and curve II represents the discharging for the nitrous oxide of colder fuel-air mixture layer.As can be seen, in same burner, NO
2Can be in the level of 1ppm and 10ppm and Geng Gao.Curve III represents the situation for even temperature scatter chart in heated fuel and the air Mixture before igniting.
Attempt by hotter gas is incorporated into the inhomogeneities of eliminating temperature in fresh fuel and the air draught, can cause such fact, promptly, with can expectable situation opposite, accept the fuel of hotter combustion product and the part of air Mixture and compare, can be heated to lower temperature with the remainder of the gaseous mixture of accepting less combustion product.This can make an explanation with the following fact,, crosses the combustion product of the heat of volume that is, causes stronger fuel reformation, and this is the reason that causes temperature to reduce.For the bad mixing of fuel and air, this phenomenon becomes more remarkable, therefore, owing to higher reformation speed, has the zone of the air-flow of higher fuel level, the reduction of temperature even lower.This can be as seen from Figure 4, and Fig. 4 represents the function of speed relation of temperature in fuel and the air Mixture air-flow and vortex periphery.As can be seen, temperature in fuel and air draught rises to be increased always, becomes up to the speed of vortex periphery till 1.2 to 1.25 times of inlet fluid flow velocity, and temperature descends after this point, although will a large amount of heat energy be injected into during inlet fluid flows.
Therefore, clearly, the inhomogeneities of temperature recited above remains to the moment of igniting always in fuel and air draught.When fuel and the igniting of Air mixing gas, colder part will earlier burn down, and becomes than igniting is not hotter than the part of heat before.For reducing the peripheral speed of the desirable vortex of discharging, because reintegration described above, in fuel that is burning and air Mixture (after igniting), the inhomogeneities of temperature even become higher.This can be explained with the following fact, that is, the part of heat of fuel and air Mixture after the burning of the colder part of gaseous mixture has been finished, also will burn away.At this moment temperature non can be up to about 500 ℃.
Difference between the combustion process recited above is explained by the different combustion chemistry in the air-flow injection stream with different temperatures (flow jets).Because colder jet comprises more combustion product, so the oxidation rate of the CO in these jets is determined by the known one-level chemical equation of those skilled in the art:
x＝a
1-b
1[exp(-kt)] (1)
Wherein:
X is the present CO level (mol) in combustion product;
a
1It is initial CO level (mol);
K is the kinetic constant (2.15mol/s) of reaction;
b
1It is temperature coefficient
T is the time (s) of burning.
The air-flow injection stream that includes the heat of less combustion product is burnt according to the secondary chemical equation, and this equation has reflected in this injection stream, spreads the influence of quality transmission to the combustion process in this injection stream:
x＝a
2-b
2[exp(-kt)]+Deff[exp(-mt
2)] (2)
Wherein:
X, a
2, b
2, k and t have and x, a
1, b
1, k and t synonymous;
Deff is effective diffusion cofficient (mol/cm
2* s);
M is non-binary collision coefficient (cm
-1* s
-1).
Below with reference to Fig. 5 this two equational working methods are described, this Fig. 5 represents the concentration (%) of CO and CH and the functional relation of burning time.The dynamics that curve I representative is described by equation (1), as can be seen, fuel after-flame apace in very short burning time, this helps reducing NO
xDischarging, have minimum CO level simultaneously.Curve II represents the dynamics by equation (2) description, and as can be seen, combustion process adds higher ignition temperature than the much longer time of the previous case cost, causes high NO
xDischarging, and the after-flame of very slow CO.Should be pointed out that curve II provides under the ideal situation of the fuel of supposing homogeneous and Air mixing gas.For obtainable fuel and air Mixture in the burner of prior art, the result will be poor a lot.
In order to eliminate above-mentioned shortcoming of the prior art, need on the entire cross section of the inlet that fluid stream is imported to burner, to improve the temperature of primary air air-flow equably just in time in the porch of combustion zone.Importantly, before entering the combustion zone, the air-flow main body of whole introducing all receives substantially the same heat energy basically.If situation is that like this for the entire body of fuel and Air mixing gas, the fuel the condition of reorganization is identical basically.
The advantage of this method is as described below.Because the air-flow of being lighted a fire did not have the inhomogeneities of temperature before fuel and air Mixture igniting, so, on whole air-flow main body, burn in identical temperature basically, in this case, be in maximum design set-point temperature at burner outlet, for example, it is 1200 ℃, in burner, on any point, temperature can be at this more than level.Known, this is minimum NO
2Formation temperature and the after-flame temperature of the most violent CO.When being used for gas-turbine unit, this feasible ignition temperature that burner design can be become equal TIT.Even temperature scatter chart in the combustion zone guarantees not have the burner region of heat spot and hot-spot, therefore, makes that the manufacturing of burner is more cheap and simpler, and prolongs the life-span of burner.
The uniformity of the temperature distribution history in the air-flow of introducing makes burner one of can utilize in equation (1) or the equation (2) operation well.As shown in Figure 4, for the speed of vortex periphery until during 1.2 times of the speed of inlet fluid stream, combustion process mainly takes place according to equation (2), has low NO at the burner outlet place
xDischarging, and relatively low CO discharging.For the velocity ratio between 1.4 and 2, NO at the burner outlet place
xWith all very low (see figure 5) of the discharging of CO.
Preferably, at entrance area, the temperature of the air that will be used to burn improves 50 ℃ to 550 ℃.If the requirement of CO discharging is not too strict, can use higher temperature rise, this will greatly simplify the design of burner.In this case, equation (2) will determine burn operation, and this process does not require the hot gas of a large amount of recirculation, and this has reduced the thermic load of combustor component.If require low CO level, then can reduce temperature rise, but, should increase in but, in 1.4 to 2.2 scope, work at the ratio of speed with the speed of the primary air that enters the introducing in the primary air zone of the vortex periphery of the outside of boundary layer near the zone of inlet.In this case, burner has low NO according to equation (1) work
xDischarging, the CO level then significantly reduces, shown in the curve I among Fig. 5.
In near the zone of inlet but at the ratio of speed with the speed of the primary air that enters the introducing in the primary air zone of the vortex periphery of the outside of boundary layer, in 1.4 to 2.2 scope.As described above, between the temperature rise of this ratio and inlet fluid stream, exist certain relation.As existing two zones as seen from Figure 4, a zone is by equation (2) control, and another zone is controlled by equation (1).Be similar to transitional region between 0.8 and 1.5 at ratio value, describe by two equations (1) and (2), at this zone, NO
xLevel is higher than the level of left field and right side area, and the level of CO only is higher than the zone on right side.This transitional region for example takes place under the situation of transient state, and, for example can be by changing speed proportional (for example by change the entrance cross-section area or at the angle beta at burble point place) with its elimination.
According to burner of the present invention, can utilize the turbulizer in the downstream of the outlet that is arranged on the combustion space to make, so that improve the oxidizing condition of residual CO.In this case, burner can be according to equation (2) with low ignition temperature work, and still have good CO discharge performance.When working according to equation (1), can adopt identical equipment in order further to reduce the CO level.
Fig. 6 represent to be applied to spray burner according to burner of the present invention, Fig. 6 is a cutaway view.As shown in Figure 7, this burner has an elongated structure, can make the needed length in furnace wall that for example is used to cover boiler plant.Burner by label 10 expressions has the shell that is limited by wall 12 (also can play a part lining).Wall 12 and end wall 14 (only expressing a right side wall 14 in Fig. 7) limit burner space 16, and the burning of fuel takes place in this space.Combustion space 16 has inlet 18 and the outlet 20 that is spaced apart from each other, and, should be appreciated that fluid (for example being in the air under the pressure) is by entering the mouth 18 with speed V
1Be directed in the combustion space 16, and on outlet 20 direction, moving, so that be used in the device (not shown) in a downstream that is arranged on burner 10 by combustion space 16.According to the present invention, burner space 16 has a circular wall 21, and this circular wall limits the path that is used to recycle eddy current, and described eddy current is separated from the fluid stream of discharging by the outlet 20 of combustion space 16.The part of fluid stream, before it was discharged from combustion space 16 by outlet 20,22 places separated from fluid at burble point, and circular surface 21 extends between burble point 22 and exit region 24, and wherein, outlet 18 is positioned at this exit region 24.Here employed term " circle " refer to " appearance profile " with an accurate or approximate circle (Webster ' s Third New International Dictionary of the EnglishLanguage, Merriam-Webster, Inc.).Should be appreciated that for the present invention accurate circle is preferably, still, is similar to round shape, for example ellipse etc. also can be used to reach purpose of the present invention.Inlet fluid stream moves along the path of representing with line O-O by combustion space 16.Between the direction of motion of inlet fluid stream and part 26 at the wall 12 at inlet 18 places or and the direction of the recirculation vortex at 18 places that entering the mouth between angle [alpha], preferably between about 85 ° and 175 °, be expressed as a right angle here.The effect of this angle will be described below.At the direction of motion O-O of inlet fluid stream with between separation/tapping point 22 place and wall 12 tangents the plane T-T or the angle beta between the direction at the recirculation vortex at O-O direction and tapping point 22 places, preferably between about 100 ° and 15 °.The effect of this angle will make an explanation below.Size a, b, c, d and r, superincumbent according to carrying out explanation in the description of combustion method of the present invention.
Burner moves in such a way.For example by air blast or compressor, 18 import the fluid that is used to burn such as air etc. by entering the mouth, should be appreciated that the air that can be pre-mixed with fuel imports, perhaps can fuel be fed to individually during fluid flows at the porch (not shown).This fluids that import by inlet 18 16 move to outlet 20 from the combustion space along O-O direction substantially, and the initial velocity of this fluid stream is V
1(not shown by igniter, for example, can be installed in the upstream of inlet 18 or be installed in combustion space 16 interior) with fuel ignition, and beginning is 16 internal combustion in the combustion space, cause forming the combustion product of heat, these combustion products are discharged by outlet 20, for example, be used in the boiler or any other heat-exchange device in.
Preferably, igniter should not be arranged on recirculation vortex in, with avoid with the zone in the fluid flow disturbance.In the embodiment of can-type chamber, the flame tube (cross-firetube) that crosses can contact with jar at such some place, at described point, each jar is outside the recirculation regions or in (but not within recirculation regions, as implementing traditionally sometimes) before the recirculation regions.Perhaps, igniter even also can be configured in the recirculation chamber, if with its correct so as basically not with the fluid flow disturbance.Before combustion product (hot gas) left combustion space 16, their part was separated from the primary fluid stream of moving along the O-O line basically at burble point or tapping point 22 places, so that form the recirculation eddy current by 28 expressions of the arrow among Fig. 6.This eddy current has speed V
2, the ratio of this speed dependent between the inside dimension of combustion space 16 simultaneously, also depends on along the characteristic of the recirculation eddy current of circular surface 21.For the direction of motion O-O that flows at burble point 22 place's inlet fluids and for the situation that the angle beta between the positive section T-T of wall 12 is 45 °, turbulence level along the eddy current of circular surface 21 is about 0.008, if angle beta is 100 °, turbulence level is about 0.2.The preferred value of angle beta is 65 °, and turbulence level is about 0.03 to 0.025.Be to be understood that, have only when with circular surface 21 (at least from burble point 22 beginning and along this surface of extending towards the direction of inlet 18 major part) when making very smoothly, the very low value of the turbulence level that can obtain to provide above, that is, without any hole, groove, projection, fluid intake etc.In this lip-deep any this scrambling, all will be for certain, disturbance 21 eddy current surfacewise inevitably, with its turbulent flowization, turbulence level is risen, surpass above-mentioned boundary, reach 0.2 even higher, make it similar to what happens in traditional closed-type scroll burner.When application need, can increase turbulence level (in the above in Gui Ding the limit), so that increase the temperature of vortex.According to the condition that recirculation flow and inlet stream meet in the zone 24 of inlet 18, selected angle α in 85 ° to 175 ° scope.The increase of the numerical value of this angle causes turbulent flow lower when two fluid streams meet.When having speed V
2The recirculation eddy current run at entrance area and have speed V
1Inlet fluid when stream (V
2＞V
1), as in the above for illustrate when the process that takes place in the combustion space 16 described in detail like that, two fluids flow and limit boundary layer between them.Should be appreciated that because hot nozzle effect described above, and because along the low turbulence level of circular surface 21 and there is not the element of turbulent flowization along this path, so, as mentioned above, speed V
2Greater than speed V
1, flow till the moment that entrance area meets higher speed V up to two fluids
2Keep to such an extent that be higher than speed V always
1
Fig. 8 represents the part schematic sectional view according to annular burner of the present invention, for representing with equal reference number with Fig. 6 and 7 same parts, still, adds 100 on reference number.In the present embodiment, inlet fluid has part 132 along its surface 130 of flowing at inlet 118 places, and this part 132 tilts with 0 ° to 15 ° angle γ with respect to the roughly direction O-O of inlet fluid stream.This structure can be used for requirement and keep speed V
1And V
2Between ratio, and in the limited application of the radial dimension of burner.In this case, the V that can not underspeed by the area of section of amplifying b simply and increase inlet
1, stream and the interference of hanging down turbulent recirculation eddy current because this will cause entering the mouth.By adopting angle γ, can make size b in fact constant, but make the area of section of fluid stream bigger, and can not disturb with the recirculation eddy current greater than 0 °.As for others, present embodiment moves according to top mode with reference to Fig. 6 and 7 described embodiment.
Fig. 9 is according to the longitudinal section of the annular burner of Fig. 8 design, for representing with equal reference number with Fig. 6 and 7 same parts, still, adds 200 on reference number.Here, its difference is, makes angle [alpha] bigger, provides low turbulent-flow conditions as mild as a dove for two fluid streams (recirculation eddy current and inlet fluid stream), so that reduce the CO level.
How the embodiment of the burner shown in Figure 10 presentation graphs 8 with adding that 300 equal reference number represents, is used for illustrating that the embodiment with Fig. 8 and burner shown in Figure 9 uses together for same part.Here, as can be seen, angle γ is greater than 0 °, and angle [alpha] is greater than 90 °.For burner,, can reduce the level of CO for the burner of little radial dimension according to such design of the present invention.
Figure 11 represents the tubular burner of the design according to the present invention.For same part with adding that 400 equal reference number represents.The difference here is, inlet stream is imported into along radial direction, and along the path O of bending
1-O
1 Motion.The wall 434 that limits surface 430 can be moved into and shift out (left from figure is to right-hand, and vice versa) in guide pin bushing 436.This makes can be used for different purposes with same burner, because by changing entry condition, can change speed V
1And V
2Ratio, therefore, change the maximum temperature of the design point of burner.Also wall 434 can be configured to move in the middle of the operating process of burner (by unshowned mechanism), in this case, for example, can change the maximum temperature of burner according to loading condiction.
Figure 12 and 13 expressions are according to the embodiment of burner of the present invention, wherein, 18 change entering the mouth.As shown in figure 12, inlet has a projection 13 that radially extends internally, and described projection was arranged along the circle spacing of opening, and in Figure 13, inlet has radial groove 15, and described groove 15 was arranged along the circle spacing of opening.In both cases, projection and groove are guaranteed the structure of the outer peripheral face that the fluid introduced flows by increasing its surface area.This make it possible to with the speed V of two fluids stream
1And V
2Between identical ratio, enlarge inlet fluid stream peripheral with the contact area that recycles between the eddy current.By this configuration, can make burner shorter, perhaps strengthen two interactions between the fluid stream with the identical length of burner.
Figure 14 represents to be combined with the longitudinal section according to the gas-turbine unit of annular burner of the present invention, and wherein, the part that is equal to is with adding that 500 identical reference number represents.Annular burner 510 is described and the burner of expression constitutes similarly basically and with reference to Figure 11, and this annular burner 510 is installed in the gas-turbine unit, expresses the turbine that has one group of nozzle 541 540 that is installed on the axle 542 among the figure.By conduit 519 air is offered the inlet 518 of combustion space 516 from the compressor (not shown), be supplied to burner.Inlet 518 has diffuser 544, and this diffuser keeps having passed to the remaining circumference vortex of air draught, so that improve the outer surface of the intake air air-flow in the combustion space 516 and the interaction between the recirculation eddy current 528.Through port 546 imports to fuel in the combustion space 516, so that be pre-mixed with air.Should be appreciated that fuel can be pre-mixed at the upstream and the air of burner.In the entrance area 524, in wall portion 526, the other inlet that is used for air and/or fuel by 548 expressions is set, so that the recirculation eddy current be about to meet by the periphery of 518 air draughts that import that enter the mouth before, change the structure of described recirculation eddy current.If burner design is become in low ignition temperature work, for example 1000 ℃, through port 548 adds air and fuel, can cause temperature is brought up to for example 1500 ℃.On the contrary, if burner design is become to work under 1500 ℃ temperature, through port 548 provides extra air, can obtain 1000 ℃ lower temperature.Air and fuel can provide with controlled amount and controlled ratio by through port 548, so that under the condition of fluctuation, around certain set-point, burner are remained on any required temperature.Burner has another one with 550 inlets of representing that are used for combustion air, so that fresh air (for example oxygen) is added in the combustion product, described combustion product is used for turbine 540 from separating by exporting the 520 hot gas streams of discharging.If equivalent proportion is too low, exhaust stream needs more oxygen, is used for oxidation CO.The composition CH and the CO of the incomplete oxidation that comprises fuel if the equivalent proportion work that burner ether is high, exhaust fail to be convened for lack of a quorum in this case, add fresh air, can strengthen oxidation reaction, even improve delivery temperature.Should remark additionally, through port 550 adds air, can and strengthen the CO after-flame with exhaust stream turbulent flowization.Obviously, also the turbulizer of the known special use of those skilled in the art can be installed to the downstream of the outlet of combustion space.Be to be understood that, above-described through port 548 adds the step that air and/or fuel and through port 550 add air, can finish by the control system that utilization has load and/or temperature sensor and a suitable control device, described control system is utilized those skilled in the art's known method and equipment, is used to change, connect or close the supply of additional air and fuel.
Figure 15 is that expression is combined with the longitudinal section according to the another one embodiment of the gas-turbine unit of annular burner of the present invention.This embodiment utilizes centrifugal compressor 600 and the centripetal turbine 610 on the shared rotor disc 612, described rotor disc be installed in axle journal be bearing on the shell 615 the axle 614 on.Burner 616 according to the present invention has shell 618 and the lining 619 that limits combustion space 620, and described combustion space 620 has inlet 622 in compressor side, has outlet 624 in turbo-side.Burner has igniter 626.Spaced walls between compressor 600 and turbine 610 has the circular surface 630 that is used to recycle eddy current, and extend between the inlet 622 of burble point 632 that exports 624 places and combustion space 620 on this surface.Can obviously find out by Figure 16 (this figure is the view that the arrow XVI along Figure 15 gets), by along O
2-O
2The recirculation eddy current that the part of the combustion product of line, arrow 634 motions forms in this case, is positioned at the inside of inlet stream, and described inlet flows on identical direction to that indicated in the drawings along path O
2-O
2Motion.For the eddy current turbulent-flow conditions with on regard to for the identical situation of condition that previous embodiment describes, the extra advantage here is, this air-flow is gone up motion at " gas lubricant " that fuel and Air mixing entraining air stream provide, and this will reduce hydraulic slip and heat loss simultaneously.As can be as seen from Figure 17, circular surface 630 be by blade 636 (the being shown in Figure 16) section of being divided into, and described blade is with the longitudinal axis O of fluid stream around engine
3-O
3Peripheral speed convert vortex velocity V to
2
Should be noted that the ratio (V of vortex velocity to inlet flow velocity degree
2/ V
1) influential for the CO level in the exhaust.Figure 18 represents, for three kinds of different V
2/ V
1Ratio, the functional relation of the CO concentration and the time of staying (ms).As can be seen, best solution is to have the highest velocity ratio, such as 2.2, still, in this case, the highest temperature that can obtain reduces.This means that require in the application of high temperature at burner outlet, the ratio that should underspeed is accompanied by increasing of CO concentration.The method that can be used to control higher CO concentration has been discussed above.
Produced prototype, and it has been tested according to annular burner of the present invention.A burner # 1 has 760cm
3Capacity, with the possible speed V of maximum
2Burn.Maximum temperature in burner is about 1650 ℃.Another one burner # 2 has 690cm
3Capacity, with a preferred speed V
2Burn, guarantee about 1260 ℃ maximum temperature.Burner has following specification:
Inside diameter 100mm
Flow 0.06kg/s
Pressure 1.2kg/cm
2
T
exit 650-1260℃
In the natural gas of burning, test, provide following result:
Burner is guaranteed stable igniting, need not the structure of special starting fuel mixture.
Burner is guaranteed stable cold start, need not any preheating.
After 500 start cycles, the metal in the burner does not demonstrate the sign of any damage.
In the scope of the whole burning condition of equivalent proportion from 0.7 to 0.17, stable burning.
Under from 0.7 to 0.17 situation of equivalent proportion, during whole test in, not observing in exhaust can observable particulate matter.
Some result of the test provides as follows.
Table 1--is for prototype burner #1 (760cm
3) emission testing
| Discharging | The burner outlet temperature, ℃ | |||
| 650 | 1,100 | 1,370 | 1,650 | |
| NO x | 0 | 2-3ppm | 4-5ppm | 10ppm |
| CO | 150 | 30ppm | 12ppm | 5ppm |
Annotate: all data from table 1 to table 4 are the O of reference 15% all
2
Table 2 is for prototype burner # (690cm
3) the CO emission test results
| Temperature, ℃ | 1,005 | 1,090 | 1,145 | 1,175 | 1,190 | 1,220 | 1,220 | 1,245 |
| The CO discharging, ppm | 449 | 263 | 93 | 53 | 38 | 15 | 7 | 0 |
Table 3--is for prototype burner #2 (690cm
3) CO emission test results (gas analyser 400HCLD)
| Temperature, ℃ | 765 | 875 | 975 | 1,030 | 1,065 | 1,195 | 1,130 | 1,150 | 1,190 | 1,210 |
| NO x，ppm | 1.37 | 1.53 | 1.65 | 1.36 | 1.45 | 1.79 | 1.41 | 1.61 | 1.81 | 1.97 |
| NO 2，ppm | 0.11 | 0.06 | 0.07 | 0.03 | 0.03 | 0.05 | 0.04 | 0.02 | 0.05 | 0.08 |
The NO that table 4--obtains when utilizing more accurate API200A gas analyser
xEmission test results; Burner #2 (690cm
3)
| Temperature, ℃ | 835 | 940 | 985 | 1,045 | 1,100 | 1,180 | 1,205 | 1,225 |
| NO 2，ppm | 1.06 | 1.49 | 1.25 | 0.995 | 0.988 | 1.19 | 1.42 | 1.73 |
Utilization has the fuel of following composition the prototype burner is tested:
Methane 15-22%abs.
Nitrogen 10-30%
Carbon dioxide 20-25%
Water (steam) is until 40%
Other gas is until 7%.
Result of the test and on regard to coming to the same thing shown in the natural gas.
For a concrete burner (seeing Figure 22), utilize the equivalent proportion of standard, directly combustion reaction is preponderated than back reaction.But, the back reaction that fuel is reformed takes place in the superficial layer of vortex, in this case, this process is accompanied by the reduction of the temperature of vortex, consequently causes the temperature of burner wall (along air-flow) to reduce.See Table 6.
Should be noted that CH in the boundary layer of eddy current and fuel and air draught
4And O
2The variation of concentration, not only influence the thermal energy transfer process, but also influence the Direction of Reaction (directly reaction and back reaction).If CH in fuel and Air mixing gas
4Concentration greater than the normal concentration (as comparing the result that the coefficient of equivalence increases) of burning with the design set-point, the fuel reforming process will begin to preponderate in boundary layer.Combine with the ratio of the oxygen of supplying in vortex, this will cause the reduction of vortex peripheral temperature, thereby the temperature that arrives the molecule of vortex center also will descend.Simultaneous these two processes will cause the temperature of vortex to be reduced to a subcritical value, cause flame-out.This be why as doing in the past the simple mechanical mixture by eddy current and fuel and air Mixture can not solve one of smooth combustion reason of lean mixture, because, in this case, provide heat energy, be accompanied by and increase CO simultaneously to fuel and air Mixture
2And H
2The supply of O (fuel that causes strengthening is reformed), the temperature of vortex and fuel and air Mixture reduces simultaneously.But, because the reaction that takes place in the layer of border " interface " in the present invention according to burner of the present invention, can stably be operated under this condition.See Table 7.The operation of this " reformation pattern ", even under the situation that does not have flame, can stably and continuously carry out.
Table 5 and 6: for having ML burner, burning #2 (690cm
3) stability test result (test finish) with gaseous fuel.
Table 5:
| Test # | Initial fuel flow rate, sl/m (φ=0.5) | The fuel flow rate value of smooth combustion, sl/m * | Flame-out fuel flow rate | |||||
| sl/m | t， | |||||||
| 1 | 60 ** | 50 | 45 | 40 | 35 | 30 | 26.9 | 325 |
| 2 | 52 | 45 | 41 | 36 | 30 | 27 | 23.1 | 323 |
| 3 | 45 | 40 | 32 | 28 | 25 | 23 | 19.1 | 325 |
| 4 | 40 | 33 | 29 | 25 | 21 | 19 | 16 | 330 |
| 5 | 35.5 | 30 | 26 | 22 | 20 | 18 | 15 | 331 |
| 6 | 30 | 29 | 23 | 19 | 18 | 16 | 13.2 | 330 |
*Per minute standard liter.Equivalent proportion is not determined.Have only fuel flow rate to change, air mass flow remains unchanged
*60sl/m is for 690cm
3Burner be preferred Fuel Consumption.
Table 6:
| Point # | TIT (the burner outlet temperature, ℃) | ||||
| 1000 | 1150 | 1200 | 1250 | 1270 | |
| 1 | 600 | 612 | 619 | 630 | 635 |
| 2 | 610 | 618 | 622 | 639 | 655 |
| 3 | 576 | 582 | 617 | 625 | 649 |
| 4 | 551 | 560 | 585 | 610 | 645 |
| 5 | 527 | 536 | 559 | 583 | 620 |
| 6 | 503 | 510 | 535 | 560 | 590 |
| 7 | 471 | 479 | 509 | 537 | 547 |
| 8 | 452 | 458 | 475 | 491 | 520 |
| 9 | 442 | 447 | 456 | 473 | 495 |
| 10 | 436 | 441 | 448 | 469 | 487 |
| 11 | 620 | 625 | 631 | 648 | 663 |
Annotate.The temperature of metal is measured on the outer surface of metal, because lining is without any cooling.
Table 7:
| Fuel flow rate, sl/m | CO 2，％ | CO，％ | HC，ppm | O 2，％ | T3， | Blast | |
| 120 | 3,31 | 2,35 | 250 | 12,25 | 460 | 0 |
The preferred embodiments of the present invention have been described above.But, should be appreciated that for the embodiment that is proposed here and can carry out various remodeling and change, and do not exceed the spirit and scope of the present invention defined in appended claims.
Claims (37)
1. burner comprises:
Reactor;
Inlet is used for primary fluid stream is imported in the described reactor;
Outlet is used for heated fluid is discharged from described reactor;
Described reactor and comprises between described inlet and described outlet: primary fluid stream zone, the major part of described primary fluid stream along the primary fluid stream path by this zone; Recirculation regions, the less part of described primary fluid stream is by this recirculation regions;
Wherein, described recirculation regions is partly limited by a wall, described wall has with continuous basically mode curved inner surface and from extend to the reentry point near described inlet near the tapping point of described outlet in one direction, described inner surface is shaped in such a way and locatees with respect to described primary fluid stream path, promptly, in the operating process of described reactor, make that the segment fluid flow in described primary fluid stream path turns at described tapping point place to form the recirculation eddy current; And
Wherein, described inner surface is further characterized in that this inner surface does not have discontinuity, is not subjected to moving of disturbance so that cause boundary layer basically along the periphery of described recirculation eddy current.
2. burner as claimed in claim 1 is characterized in that, plays a part in the operator scheme of combustion chamber at described reactor, and the volume of described recirculation regions is not less than the volume in described primary fluid stream zone.
3. burner as claimed in claim 1 is characterized in that, plays a part in the operator scheme of reformer at described reactor, and the volume of described recirculation regions is not less than the twice of the volume in described primary fluid stream zone.
4. burner as claimed in claim 1 is characterized in that, plays a part in the operator scheme of combustion chamber at described reactor, and the volume that enters the fluid of described recirculation regions is compared with the fluid of discharging in described outlet and is not less than 7 percent.
5. burner as claimed in claim 1 is characterized in that, plays a part in the operator scheme of reformer at described reactor, and the volume that enters the fluid of described recirculation regions is compared with the fluid of discharging in described outlet and is not less than 10.
6. burner as claimed in claim 1 is characterized in that the fluid in described boundary layer has the turbulence level less than 0.2.
7. burner as claimed in claim 6 is characterized in that described turbulence level is between 0.008 to 0.01.
8. burner as claimed in claim 1 is characterized in that, described recirculation flow is spent between 100 degree 15 at the direction angulation at tapping point place with respect to described primary fluid stream path in the direction at described tapping point place.
9. burner as claimed in claim 1 is characterized in that, described recirculation flow is spent between 175 degree 85 at the direction angulation at reentry point place with respect to described primary fluid stream path in the direction at described reentry point place.
10. burner as claimed in claim 1, it is characterized in that, play a part in the operator scheme of combustion chamber at reactor, near described inlet but the ratio of speed and the speed of the described primary fluid stream that enters described primary fluid stream zone of the described recirculation eddy current in the zone outside described boundary layer, in being not less than 1.4: 1 scope.
11. burner as claimed in claim 1, it is characterized in that, play a part in the operator scheme of reformer at reactor, near described inlet but the ratio of speed and the speed of the described primary fluid stream that enters described primary fluid stream zone of the described recirculation eddy current in the zone outside described boundary layer, in being not less than 2: 1 scope.
12. burner as claimed in claim 1 is characterized in that, when described heated fluid had about 1100 ℃ temperature in described exit, described boundary layer had the degree of depth of about 1mm.
13. burner as claimed in claim 1 is characterized in that, when described heated fluid had about 800 ℃ temperature in described exit, described boundary layer had the degree of depth of about 2mm.
14. burner as claimed in claim 1, it is characterized in that, when described heated fluid had temperature in 380-420 ℃ of scope in described exit, the degree of depth of described boundary layer was greater than the diameter of the centronucleus of the recirculated fluid in described recirculation eddy current.
15. burner as claimed in claim 1 is characterized in that, the fluid layering motion in described recirculation eddy current, and described layer does not radially mix in vortex basically.
16. burner as claimed in claim 15 is characterized in that, heat energy transmits from some layers of the outside of the described layer of some courses of the inside of described layer.
17. burner as claimed in claim 1, it is characterized in that, in the intersection of described peripheral eddy current with described primary fluid stream by described inlet, existence is than the high temperature of other temperature in the described reactor, after described primary fluid stream is passed through described intersection, described peripheral eddy current moves along the direction identical with described primary fluid stream, between described peripheral eddy current and described primary fluid stream, form boundary layer, and wherein, the fluid of heat energy from described peripheral eddy current passes to fluid in the described primary fluid stream zone by described boundary layer.
18. burner as claimed in claim 17, it is characterized in that, by the fluid of described inlet, in the surf zone of the close described boundary layer of described fluid, by contacting and lighted, and play a part to be used for the pilot flame of burner with described boundary layer.
19. burner as claimed in claim 17 is characterized in that, between fluid in described primary fluid stream and the fluid in described peripheral eddy current, does not have appreciable turbulent mixture.
20. burner as claimed in claim 17 is characterized in that, described boundary layer causes the hot nozzle that is established and remains in the described primary fluid stream zone.
21. burner as claimed in claim 17 is characterized in that, in the described boundary layer that described boundary layer and described primary fluid stream are met, burning and fuel takes place simultaneously reform, and in the described operating process of burner, keeps the described combination of burning and reformation.
22. burner as claimed in claim 20 is characterized in that, the cross-sectional area of described outlet is not more than 2.2 times of cross-sectional area of described inlet.
23. burner as claimed in claim 1, it is characterized in that, in order to change to the operator scheme that described reactor plays a part reformer, with respect to for the described entrance cross-section area that uses in the operator scheme of described reactor as the combustion chamber operation, reduce described entrance cross-section area.
24. the method that fuel is reacted, described burner comprises reactor; Be used for primary fluid stream is imported the inlet of described reactor; Be used for of the outlet of heated fluid from described reactor discharge; Described reactor is between described inlet and described outlet and comprise primary fluid stream zone and recirculation flow zone, said method comprising the steps of:
The major part of described primary fluid stream is passed through along described primary fluid stream zone in path;
By described recirculation regions, so that form the recirculation eddy current, described recirculation eddy current makes the part of the fluid in the described recirculation regions turn back to zone near described inlet to the less part that makes described primary fluid stream in path;
The boundary layer that makes recirculated fluid does not have to flow along the described inner wall surface of described recirculation regions basically turbulently;
The periphery and the described primary fluid stream of described recirculation eddy current are being crossed near in the zone of described inlet, and wherein, described ambient fluid stream has the speed higher than described primary fluid stream; Along the described ambient fluid stream in the described zone that crosses along moving with the roughly the same direction of described main fluid;
, basically not by mechanical mixture described ambient fluid stream is mixed with described primary fluid stream by diffusion;
Thereby, between described primary fluid stream and described ambient fluid stream, form boundary layer, and the fluid from described ambient fluid stream carries out the transmission of significant heat energy by the fluid of described boundary layer in described primary fluid stream zone.
25. method as claimed in claim 24 is characterized in that, plays a part in the operator scheme of combustion chamber at described reactor, the volume that enters the fluid of described recirculation regions is compared with the fluid of discharging in described outlet and is not more than 7 percent.
26. method as claimed in claim 24 is characterized in that, plays a part in the operator scheme of reformer at described reactor, the volume that enters the fluid of described recirculation regions is compared with the fluid of discharging in described outlet and is not more than 10.
27. method as claimed in claim 24 is characterized in that, the described boundary layer along the recirculated fluid stream of the described inner wall surface of described recirculation regions has the turbulence level less than 0.2.
28. method as claimed in claim 27 is characterized in that, the described boundary layer along the recirculated fluid stream of the described inner wall surface of described recirculation regions has the turbulence level between 0.008 to 0.01.
29. method as claimed in claim 24, it is characterized in that, play a part in the operator scheme of combustion chamber at described reactor, be not less than at the ratio of the described fair speed of described peripheral eddy current and the speed of the described primary fluid stream that enters described primary fluid stream zone in 1.4: 1 the scope.
30. method as claimed in claim 24, it is characterized in that, play a part in the operator scheme of reformer at described reactor, be not less than at the ratio of the described fair speed of described peripheral eddy current and the speed of the described primary fluid stream that enters described primary fluid stream zone in 2: 1 the scope.
31. method as claimed in claim 24 further comprises the fluid layering motion that makes in the described recirculation eddy current, wherein, described layer does not radially mix in vortex basically.
32. method as claimed in claim 24 is characterized in that, the layer of some outsides in the described layer of heat energy some inner courses from described layer transmits.
33. method as claimed in claim 24, further comprise making the fluid that enters by described inlet, in surf zone, by contacting and lighted with described boundary layer near the described fluid of described boundary layer, thereby, play a part to be used for the pilot flame of burner.
34. method as claimed in claim 24 further comprises the fluid in described primary fluid stream is mixed with fluid in described peripheral eddy current, and do not cause tangible turbulent flow.
35. method as claimed in claim 24 further comprises making in described primary fluid stream zone and setting up and keep hot nozzle.
36. method as claimed in claim 24 further comprises making that burning and fuel take place simultaneously to be reformed in described boundary layer, and the described combination that keeps burning and reform in the operating process of burner.
37. method as claimed in claim 24 further comprises, by reducing the cross-sectional area of described inlet, the operator scheme that described reactor is played the combustion chamber effect changes to the operator scheme that described reactor plays reformer.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US50840503P | 2003-10-03 | 2003-10-03 | |
| US60/508,405 | 2003-10-03 | ||
| US58595804P | 2004-07-06 | 2004-07-06 | |
| US60/585,958 | 2004-07-06 | ||
| PCT/US2004/028040 WO2005040677A2 (en) | 2003-10-03 | 2004-08-27 | Combustion method and apparatus for carrying out same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1875219A true CN1875219A (en) | 2006-12-06 |
| CN1875219B CN1875219B (en) | 2011-10-05 |
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ID=37484925
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2004800318945A Expired - Fee Related CN1875219B (en) | 2003-10-03 | 2004-08-27 | Combustion method and apparatus for carrying out same |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1875219B (en) |
| UA (1) | UA87669C2 (en) |
| ZA (1) | ZA200602687B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102713202B (en) * | 2009-09-13 | 2015-07-22 | 贫焰公司 | Combustion cavity layouts for fuel staging in trapped vortex combustors |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1011670B (en) * | 1955-06-03 | 1957-07-04 | H C Ernst Schmidt Dr Ing Dr Re | Annular mixing or combustion chamber, especially for gas turbines |
| FR1472393A (en) * | 1965-03-11 | 1967-03-10 | Gen Electric | Combustion process and device |
| US3303643A (en) * | 1965-10-22 | 1967-02-14 | Melville W Beardsley | Method and structure for supplying and confining fluid in a reaction chamber |
| DE2937631A1 (en) * | 1979-09-18 | 1981-04-02 | Daimler-Benz Ag, 7000 Stuttgart | COMBUSTION CHAMBER FOR GAS TURBINES |
| CA1191702A (en) * | 1981-10-22 | 1985-08-13 | Gaston Lavoie | Engine |
-
2004
- 2004-08-27 CN CN2004800318945A patent/CN1875219B/en not_active Expired - Fee Related
- 2004-08-27 UA UAA200604782A patent/UA87669C2/en unknown
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2006
- 2006-03-31 ZA ZA200602687A patent/ZA200602687B/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102713202B (en) * | 2009-09-13 | 2015-07-22 | 贫焰公司 | Combustion cavity layouts for fuel staging in trapped vortex combustors |
Also Published As
| Publication number | Publication date |
|---|---|
| UA87669C2 (en) | 2009-08-10 |
| CN1875219B (en) | 2011-10-05 |
| ZA200602687B (en) | 2007-07-25 |
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