EP2041492B1 - Brenner mit einstellbarer richtung und/oder öffnung der flamme und dessen verwendung - Google Patents

Brenner mit einstellbarer richtung und/oder öffnung der flamme und dessen verwendung Download PDF

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Publication number
EP2041492B1
EP2041492B1 EP07823552.0A EP07823552A EP2041492B1 EP 2041492 B1 EP2041492 B1 EP 2041492B1 EP 07823552 A EP07823552 A EP 07823552A EP 2041492 B1 EP2041492 B1 EP 2041492B1
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EP
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Prior art keywords
jet
flame
axis
primary
burner
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EP07823552.0A
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English (en)
French (fr)
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EP2041492A2 (de
Inventor
Bernard Zamuner
Nicolas Docquier
Bernard Labegorre
Thomas Lederlin
Thierry Poinsot
Vincent Faivre
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Centre National de la Recherche Scientifique CNRS
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Centre National de la Recherche Scientifique CNRS
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Priority to PL07823552T priority Critical patent/PL2041492T3/pl
Publication of EP2041492A2 publication Critical patent/EP2041492A2/de
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Publication of EP2041492B1 publication Critical patent/EP2041492B1/de
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23DBURNERS
    • F23D14/00Burners for combustion of a gas, e.g. of a gas stored under pressure as a liquid
    • F23D14/46Details, e.g. noise reduction means
    • F23D14/84Flame spreading or otherwise shaping

Definitions

  • the present invention relates to a burner for varying the direction and / or the opening of the flame, said burner comprising at least one injection channel of at least one main or primary jet and at least one injection channel. an actuator or secondary jet.
  • the primary jet is typically a jet of oxidant and / or fuel and / or an oxidant-fuel premix.
  • the majority of industrial furnaces or boilers use burners that operate in non-premixed combustion mode, ie in which the oxidant and the fuel arrive separately to the combustion site.
  • the mixture of the fuel and the oxidant is then carried out, in part (attachment of the flame in a quarry block or a prechamber) or in whole, inside the combustion chamber.
  • This mixture is controlled by the design and operating parameters of the burner, and determines the performance of the burner (operating range, heat transfer to the load to be heated, emission of pollutants, etc.).
  • the burner design determines the interaction conditions of the different jets or flows of oxidant and fuel used by the burner. Once the burner is completed, only the operating conditions can be modified. This is also true for so-called "premix" burners in which the oxidant / fuel mixture is produced in the burner upstream of the furnace.
  • the reagents are then injected by a single tube.
  • the operating conditions of industrial combustion processes may change over time. This is by nature the case of intermittent processes but it is also the case of continuous processes for which the characteristics of the charges to be heated can vary according to the production needs. This is more generally the case for any production unit subjected to aging or sensitive to the variable conditions of their environment.
  • Some combustion technologies allow discrete modes and in very limited number of operation. This is for example the case of so-called "double pulse" burners that use two different injection systems depending on whether one wants to operate the burner at low or high pulse. These two modes of operation make it possible to increase the range of operation or use of the burner or to modify for a given operating point the length of the flame.
  • the modifications of the point and / or the mode of operation are most often insufficient to optimize under all conditions the performance of the burners or processes using these burners.
  • the cyclic introduction into a solid-temperature melting furnace at ambient temperature will cause the operator (or the control system) to increase the heating power so as to obtain the fastest possible melting (with a view to 'increase productivity', but without degrading the melt load (product quality) or overheating the oven (equipment life).
  • This compromise between productivity and quality and / or life depends in particular on the ability of the system to transfer energy to the load, avoiding local overheating thereof or furnace refractories. This compromise results in a melting time below which any productivity gain will be counterbalanced by a degradation of the quality of the product or by reducing the life of the oven.
  • the maximum deflection of the flame is in practice limited to about 15 ° from the median position to the extreme position (not more than 30 °), not allowing the incident flame to scan a large surface of a charge and the construction of the corresponding burner is relatively heavy since it requires a plurality of orifices for the primary oxidant jets and a plurality of orifices for the secondary oxidant jets.
  • EP-A-0545357 describes an atomization nozzle for changing the direction of an atomized flow.
  • the nozzle comprises an atomization duct whose upstream portion has a constant cross section and whose downstream portion has an increasing cross section.
  • a supply pipe for the fluid to be atomized, said pipe terminating upstream of the outlet of the atomization duct.
  • the atomizing gas is injected into the atomization duct around the fluid pipe to be atomized.
  • the atomizing nozzle also has at least one control gas inlet for injecting control gas into the atomization duct so as to create a pressure differential in the atomizing gas and thereby change the direction of the atomized flow. obtained by atomizing the fluid to be atomized with said atomizing gas.
  • the subject of the invention is a burner allowing a great variation of the direction and / or the opening of the flame and this without having to interrupt the burner or oven operation.
  • the invention also aims to allow such variation with an optimized robust burner.
  • the invention proposes to control the direction and / or the opening of a flame by the interaction of a jet of fluid (called primary jet or main jet) with at least one other jet of fluid (called secondary jet or jet actuator), the interaction between the jets occurring inside the means delivering this main jet (tube, aperture, etc.) before said main jet emerges from said means.
  • a jet of fluid called primary jet or main jet
  • secondary jet or jet actuator the interaction between the jets occurring inside the means delivering this main jet (tube, aperture, etc.) before said main jet emerges from said means.
  • the burner according to the invention comprises a passage for bringing a primary jet towards a main outlet opening.
  • the primary jet is typically a jet containing fuel, oxidant or a fuel-oxidant premix.
  • the burner also has at least one secondary pipe for the injection of a secondary jet.
  • the fluid injected by the secondary jet may or may not belong to the same category as the fluid of the primary jet.
  • the fluid injected by the secondary jet may or may not be different from the fluid of the primary jet.
  • the secondary jet may especially be an inert jet such as water vapor or combustion products, such as recycled fumes.
  • the at least one secondary pipe opens on the passage of the primary jet through a secondary opening located upstream of the main outlet opening.
  • the secondary pipe is positioned relative to the passage so that at the point of interaction (center of inertia of the imaginary surface common to the two flows) between the secondary jet from this secondary pipe (hereinafter called: jet corresponding secondary jet) and the primary jet, the angle ⁇ between the axis of the corresponding secondary jet and the plane perpendicular to the axis of the primary jet is greater than or equal to 0 ° and less than 90 °, preferably from 0 ° to 80 °, more preferably from 0 ° to 45 °.
  • the angle ⁇ 0 °, which is preferable, the axis of the corresponding secondary jet is located in a plane perpendicular to the axis of the primary jet.
  • the at least one secondary opening is spaced from the main opening by a distance L less than or equal to ten times the square root of the section s of the main outlet opening, preferably L ⁇ 5 * ⁇ s, again from preferably L ⁇ 3 * ⁇ s.
  • the burner is provided with means for controlling the pulse of the at least one secondary jet.
  • the invention thus makes it possible to vary the direction and / or the opening of the flame coming from the burner by modifying the pulse of at least one secondary jet with said means.
  • the means for controlling the pulse of the at least one secondary jet are means for controlling the ratio between the pulse of the secondary jet and the pulse of the primary jet.
  • the invention thus makes it possible to achieve a large variation in the direction and / or opening of a flame without resorting to mechanical means, potential sources of malfunction, especially in hostile environments, such as high temperature fireplaces and / or polluted or corrosive atmosphere.
  • the control means allow in particular an active or dynamic control of the pulse of the at least one secondary jet, that is to say, they allow to vary the pulse or pulses without interrupting the burner operation / without interruption of the flame.
  • the apparatus according to the invention thus allows an equally dynamic variation of the direction and / or the opening of the flame.
  • the number of secondary jets interacting with the primary jet to obtain the desired effect on the flame will be minimized so as to limit the complexity and the cost of manufacturing the burner but also the complexity and the cost of the feed system and fluid flow control if piloting the secondary jets independently. For example, a mono-directional effect can be achieved with a single secondary jet.
  • FIG. 1 On the Figure 1 is shown a schematic diagram of the method of controlling a flame in a burner according to the invention.
  • the burner comprises a passage 10 which makes it possible to bring the primary jet towards a main outlet opening 11.
  • the primary jet is led through the passage 10 and comes to interact with the secondary jet coming from the secondary pipe 21 so as to create downstream of the outlet opening 11 a flame 1 direction and / or opening different from the direction and / or the opening of the flame in the absence of secondary jet.
  • At least one secondary pipe 21 for injecting a secondary jet opens onto the passage 10 through a secondary opening 31.
  • the distance L makes it possible to influence the impact of the secondary jets on the primary jet with identical respective pulses. For example, to maximize the directional effect, we will try to minimize this distance.
  • the length L is less than or equal to 20 cm, more preferably less than or equal to 10 cm.
  • the burner has means for controlling the pulse of the secondary jets. These means can advantageously be chosen from mass flow control devices, pressure drop control, passage section control, but also temperature control devices, control of the chemical composition of the fluid or pressure control. These means are preferably means for controlling the ratio between the pulse of the secondary jet and the pulse of the primary jet.
  • the control means enable to activate and deactivate one or more secondary jets (flow or no flow of the secondary jet concerned) so as to dynamically vary the direction and / or the opening of the flame.
  • the control means preferably also dynamically increase and decrease the pulse (non-zero) of one or more jets or increase and decrease the ratio between the pulse of a secondary jet and the pulse of the primary jet.
  • the burner can be fed with fuel and with oxidant by an oxidant injection channel and at least one fuel injection channel, arranged concentrically, or by an oxidant injection channel and at least one injection channel fuel separated from each other and preferably parallel to each other.
  • the burner advantageously comprises a block of material 5, such as a block of refractory material, in which at least a portion of the passage 10 is located, the main outlet opening 11 being located on one of the faces or surfaces of the block. : front face 6.
  • the secondary jet is conveyed by a secondary pipe 21 which passes through the block 5, this secondary jet opening preferably substantially perpendicular to the primary jet.
  • the interaction between the primary jet and the secondary jet takes place at a distance L from the front face 6 of the block from which the passage 10 of the primary jet opens, this distance L being able to vary as indicated above.
  • the invention also allows an interaction between the primary jet and one or more secondary jets so as to generate, maintain or enhance a rotation of the fluid jet resulting from this interaction and therefore the flame around its axis.
  • Such an interaction makes it possible to vary the opening of the flame.
  • the burner may be provided with at least one secondary pipe 421 to 424 which is positioned relative to the passage 410 of the primary jet such that at the corresponding secondary opening 431 to 434, the axis of the secondary jet corresponding 421 to 424 is not coplanar or substantially coplanar with the axis of the primary jet 410, this at least one secondary pipe 421 to 424 opening preferably tangentially on the passage 410 of the primary jet. In this way, the interaction between the primary jet and the secondary jet gives the primary jet a rotational pulse.
  • the burner may, in a useful manner, comprise two secondary lines 421 and 422 positioned relative to the passage 410 of the primary jet such that at the two corresponding secondary openings 431, 432, the axes of the two corresponding secondary jets 421 and 422 are not coplanar with the axis of the primary jet 410, the two secondary jets being oriented in the same direction of rotation about the axis of the primary jet.
  • the two secondary jets thus contribute to the rotational pulse imparted to the flame.
  • the two secondary openings are advantageously located on the same cross section of the passage 410 / in the same plane perpendicular to the axis of the primary jet.
  • the burner comprises at least four secondary lines 421 to 424 which are positioned relative to the passage 410 of the primary jet so that at the corresponding secondary openings 431 to 434, the axes of the secondary jets corresponding are not substantially coplanar with the axis of the primary jet.
  • Two of the corresponding secondary openings 431 and 433 are substantially coplanar with the axis of the primary jet 410 in a first plane and located on either side of the axis of the primary jet.
  • the two other corresponding secondary openings 432 and 434 are substantially coplanar with the axis of the primary jet 410 in a second plane and also located on either side of the primary axis, the four corresponding secondary jets being oriented in the same direction of rotation around the axis of the primary jet.
  • the first and the second plane may in particular be perpendicular to each other. It is also preferable that the four corresponding secondary openings are on the same cross section of the passage 410.
  • the axis of the secondary jet belongs to the plane perpendicular at this location to the axis of the primary jet, and secondly, the angle between the axis of the secondary jet and the tangent to the secondary opening (or more exactly at the imaginary surface of the passage of the primary jet at the level of the secondary opening) in this plane is between 0 and 90 °, preferably between 0 and 45 °.
  • the Figures 4a and b show an exemplary embodiment for controlling the opening of a flame.
  • the primary jet (which flows from the left to the right in the passage 410 on the figure 4a ) meets the secondary jets from the secondary lines 421, 422, 423 and 424 (represented on the figure 4b which is a cross-section along the AA plane of the figure 4a ).
  • These secondary jets impact the primary jet tangentially to the passage 410, thus allowing, according to the pulses of these different jets, "to open” more or less the flame.
  • This opening effect is essentially due to the fact that the secondary jets and the primary jet have axes that do not intersect, although the jets have physical interaction with each other. This causes a rotation of the resulting jet and therefore the flame on its axis.
  • the burner may comprise at least one secondary pipe 21 positioned with respect to the passage 10 of the primary jet so that, at the level of the corresponding secondary opening 31, this pipe has a thickness e and a height l , such that l ⁇ 0.5xe and preferably: 0.5xe ⁇ l ⁇ 5.0xe (see figure 1 ).
  • a minimum height greater than or equal to 0.5xe makes it possible to achieve an optimized interaction between the corresponding secondary jet and the primary jet.
  • the secondary pipe has a direction substantially perpendicular to the axis of the primary jet over a length l which will preferably be between 0.5 and 5 times the thickness e (dimension in the direction of the flow of the main fluid) e of said pipe (e is the diameter of the pipe when it is cylindrical).
  • this length l is greater than 5e, but this does not bring any additional effect of significant impact of the secondary jet on the primary jet.
  • the burner may comprise a quarney or a prechamber combustion (for example ceramic) disposed at the end of the passage, at least one secondary pipe being at least partially disposed within the quarl / pre-chamber.
  • a quarney or a prechamber combustion for example ceramic
  • the passage of the primary jet may consist, in whole or for at least part of it, in a primary pipe for the injection of the primary jet.
  • This primary channel leads to a primary opening.
  • This primary opening may coincide with the main outlet opening of the passage.
  • the primary pipe 308, 608 terminates before the main outlet opening 311, 611, the primary opening 309, 609 is positioned upstream of the main opening 311, 611.
  • at least one secondary opening 334 , 632, 634 may be located between the primary opening 309, 609 of the primary line 308, 608 and the main opening 311, 611 of the passage.
  • the Figure 6 is more particularly an embodiment of the invention in a tube-type burner tube having a prechamber attached to the burner inside a ceramic aperture in which the flame is stabilized (such as for example described in the applications of patents US Patent 5772427 and US Patent 5620316 in the name of the Applicant and marketed by the Applicant) under the trade name ALGLASS.
  • the starter block 605 has a cavity 671 (or prechamber) into which the bi-tube opens.
  • the passage 610 of the primary jet thus consists of a primary channel 608 opening through a primary opening 609 on the cavity 671, cavity which opens through the main outlet opening 611 located on the front face of the opening downstream of the opening primary 609.
  • the bi-tube itself is schematically constituted of a central fuel injection tube (preferably), surrounded by a concentric tube into which the oxidant is injected, the two fluids mixing in the cavity 671.
  • the passage of the primary jet will have at the level of the at least one secondary opening a fluid passage unobstructed or at least substantially unobstructed in the extension of the at least one secondary pipe corresponding, in order to allow effective interaction between the at least one corresponding secondary jet and the primary jet.
  • the cross section of the passage of the primary jet will define an unobstructed or at least substantially unobstructed fluid passage at the at least one secondary opening.
  • the Figures 3c, d and e show another embodiment of the burner, in which the primary pipe 308 terminates before the main outlet opening 311.
  • the Figure 3c represents an alternative embodiment similar to the figure 3B with however an embodiment in which there are two parallel channels (primary pipe 308 and secondary pipe 324) in a nozzle 345, the two channels 308 and 324 opening on the front face of the nozzle.
  • pellet 342 which directs the secondary jet of the secondary pipe 324 to the primary jet leaving the primary pipe 308, and more particularly perpendicular or substantially perpendicular to the primary jet.
  • the direction 344 of the flame will depend on the ratio of the pulses of the primary and secondary jets.
  • the figure 3d is an exploded view of the nozzle 345 on which is fixed the pellet 342 (by means not shown in this figure), here in the form of a hollow cylindrical portion 350 which will come to bear on the end of the nozzle 345, while the opening 346 in the pellet is positioned where opens the primary pipe 308.
  • the figure 3e represents the bottom (inside) of this pellet 342 whose inner face 349 comprises a cavity 347 in which the secondary jet coming from the secondary pipe 324 will be distributed and come to meet substantially perpendicularly the primary jet from the primary pipe 308 by the intermediate of the slot 348 above the main outlet opening 346.
  • the flame 344 ( figure 3c ) from this opening 346 will thus be deviated downwards (compared to Figures 3c, d and e ).
  • the possibility of using a pellet to give the desired orientation to one or more secondary jets before their respective interaction points with the primary jet is not limited to the secondary jets oriented so as to vary the direction of the flame, but also applies to the secondary jets described above to vary the opening of the flame.
  • the invention also relates to a method for dynamically or actively controlling the performance of a combustion system or burner with the aid of one or more secondary jets, impinging on a primary jet in order to modify the flow. of the jet and to produce a flame whose direction and / or the opening can be modified according to the characteristics (in particular direction and momentum) of the primary and / or secondary jets.
  • This method can be used to regulate in closed loop or open loop the performance of a combustion system using injections of fluid jets (liquid, gas or solid dispersion).
  • the Figure 2 represents a method of regulating the performance of a burner according to the invention 210, mounted on a hearth 212.
  • the sensors 214, 216 and 217 respectively measure quantities characterizing the products of combustion, the operating conditions of the combustion or combustion chamber and the operation of the burner. These measurements are transmitted using the lines 218, 219 and 220 to the controller 215. The latter, according to instructions given for these characteristic quantities, determines the operating parameters of the secondary jets so as to maintain the characteristic quantities at their values. setpoint and transmits using the line 221 these parameters to the control members 211 of the burner.
  • the burner according to the invention advantageously comprises means for controlling the pulses of the primary and / or secondary jets, or means for controlling the ratio of the pulses of the primary jet and the secondary jet (s).
  • This ratio is a function of the ratio of the section of the primary jet passage and the sections of the secondary pipes, the ratio of the flows in the secondary pipes to the flow of the resulting jet supplying the flame and the ratio of the densities of the fluids of the primary jet and secondary jet (s). (In the following paragraphs, when considering the variation of one of these ratios, the other two are considered constant.)
  • a ratio of sections of between 5 and 50, more preferably between 15 and 30, will preferably be chosen.
  • the ratio of the flow rate of the set of secondary jets to the total flow will typically vary between 0 (no secondary jets) and 0.5 and preferably between 0 and 0.3; more preferably between 0 and 0.15; knowing that the higher the flow ratio, the greater the deviation and / or the opening of the flame.
  • the ratio of the density of each fluid constituting the secondary jets to the density of the fluid of the primary jet makes it possible to control the impact of the secondary jets. The lower the value of this ratio, the greater the effect of the secondary jet on the primary jet, at constant flow. For practical reasons, the same fluid will often be used in the secondary jets and in the primary jet (ratio equal to unity).
  • a fluid of lower density will be used than that of the fluid in the primary jet.
  • the nature of the fluid in the secondary jets will be chosen according to the intended application. For example, to control the deflection of an air jet, it is possible to use a mixture of air and helium (of lower density) or to increase the entrainment of the products of combustion in a flame whose fuel is propane, control the main jet of fuel and / or oxidizer with a secondary jet of water vapor.
  • the ratio of densities (or densities) of the densest fluid to the least dense fluid can vary between 1 and 20, preferably between 1 and 10, more preferably between 1 and 5.
  • the geometry of the injection section of the passage and / or secondary pipes may be of various shapes and in particular circular, square, rectangular, triangular, oblong, multi-lobes, etc.
  • the geometry of these injection sections influences the development of the instabilities of the resulting jet / flame.
  • a jet output of a triangular shaped injector will be more unstable than that from a circular injector, this instability promoting the mixing of the resulting jet with the surrounding medium.
  • an oblong injector will favor in a field near the injector the non-symmetrical development of the jet unlike a circular or square injector.
  • the physicochemical properties of the fluid used to make the secondary streams they may be chosen to control certain properties of the resulting flow.
  • a mixture of main jet fuel eg natural gas
  • oxidant eg air
  • / or hydrogen or other fuel
  • a nozzle comprising a convergent / divergent
  • the Laval nozzle can also be disposed on the resulting jet before the main exit opening.
  • at least two secondary jets are used, so as to obtain a variation of the direction of the flame in a plane (for example, to the left and the right, or to the top and the bottom). It is also possible to use at least two secondary jets so as to obtain a variation of the direction of the flame in at least two secant planes.
  • These two variants alone or in combination, can scan at least a portion of a surface, such as the surface of a load.
  • a secondary jet whose axis is not secant or quasi-secant with the axis of the primary jet, the opening of the flame above the charge can be varied, alone or in combination with a scan.
  • Means for controlling the momentum of the primary jet and / or the at least one secondary jet are preferably provided.
  • the burner and process have been illustrated above with reference to one embodiment with a single primary jet that is made to interact with one or more secondary jets. It is obvious that the present invention also covers such a burner to create one or more flames whose opening and / or direction are variable from a multitude of primary jets which interact with one or more secondary jets.
  • the figure 5 illustrates how the burner according to the invention makes it possible to produce a variable flame from two primary jets: a primary jet of fuel and a primary jet of oxidant. Each primary jet interacts with one or more secondary streams. The two resulting jets from the burner, and thus also the flame, having a direction and / or a variable opening through this interaction.
  • the figure 5a schematically shows the resultant jet of fuel 61 surmounted by the resulting jet of oxidant 62, in the situation where none of these jets is controlled by an interaction with one or more secondary jets.
  • the figure 5b shows these same resulting jets, but in a situation where they are controlled or deflected in opposition (convergent jets).
  • the jet 60 is deflected downwards by the secondary jet 62 while the jet 61 is deflected upwards by the secondary jet 63, directed from below upwards (unlike 61).
  • the figure 5c shows the results in a situation where these jets are controlled or deflected in the same direction (upwards in the figure): the secondary jets 63 and 65 act from bottom to top respectively on the main jets 61 and 60, which generates resulting jets both directed upwards.
  • the secondary jets 63 and 65 act from bottom to top respectively on the main jets 61 and 60, which generates resulting jets both directed upwards.
  • the axis of the secondary jet makes with the plane perpendicular to the axis of the primary jet an angle which is less than 90 °, and preferably equal to at 0 °.
  • the channels feeding these jets are usually substantially parallel.
  • injection pad an end piece hereinafter called injection pad whose function is to transform the direction of the secondary jet initially parallel to the primary jet, a secondary jet impinging the primary jet, the axis of said secondary jet being preferably located in a plane perpendicular to the axis of the primary jet.
  • the first solution ( figure 16 ) consists in placing the burner 500 in a refractory part 501 whose geometry and the relative position burner / quarl will protect the former from excessive radiation. The position or the removal of the burner in the quarl must be sufficient to protect it from the radiation but must not limit the directional amplitude of the flame.
  • the geometry of the quarl eliminating part of it along the line 160 dotted on the figure 16 according to the angle ⁇ .
  • the ratio R / d will be in the range 0.3 to 3, while the angle ⁇ will be in the range [0 °, 60 °].
  • the second solution consists of bringing a sleeve-type refractory piece directly onto the nose of the burner (where the main outlet opening is located) as illustrated on the drawing. figure 17 . This solution eliminates the presence of a pupil with complex geometry. The dimensions of the sleeve are such that it does not limit the directional amplitude of the injector.
  • the invention also relates to a method for heating a load using a burner, wherein the direction (and / or opening) of the flame relative to the load is varied.
  • the invention makes it possible in particular to use one or at least two secondary jets, so as to obtain a variation of the direction of the flame in a plane (for example, to the left and the right, or up and down). It is also possible to use at least two secondary jets so as to obtain a variation of the direction of the flame in at least two secant planes.
  • the heating of the charge is such that, in a first phase, the flame is directed towards the charge and that, in a second phase, the flame is directed substantially parallel to the charge.
  • the injection angle of the flame can be between about 90 ° and 5 °, typically between about 90 ° and 10 °.
  • the injection angle of the flame is typically between about 5 ° and 0 °.
  • the injection angle of the flame during the first phase is between 5 ° and 75 °, more preferably 25 ° to 45 °.
  • the figure 8 shows three profiles of heat flux transferred by a flame to a charge according to the angle of incidence of the flame on the charge as a function of the distance to the injection point of the flame reactants.
  • the curves C1 and C2 respectively represent the opening angle as a function of the ratio of the actuator / main jet flows.
  • C1 relates to a CONF1 configuration in which the actuators are perpendicular to the main jet and open at a distance h from the main exit opening and C2 corresponds to a configuration identical to CONF1, but with a distance of 2xh instead of h between the secondary openings and the main exit opening.
  • the figure 9b illustrates the variations of the opening angle as a function of the ratio of the flow rates of the actuators and the main jet:
  • the figure 10B represents heat transfer to a load: heat flow delivered by a burner according to the invention, in which the ratio of the flow of the actuator jets to the flow rate of the main jet (also represented here as a percentage of the flow rate of the main jet) is varied. ), for both the fuel jet and the oxidant jet (separate injection burner). Each jet initially injected parallel to the load is progressively deflected towards the load, which increases the heat transfer to the load.
  • the Figure 11 represents a curve of the opening angle of the flame as a function of the jet pulse ratio.
  • This curve reports all the experimental data obtained for the control of the opening.
  • the measured aperture angle is plotted against the physical parameter J which is the ratio of the specific pulses of the actuator jets and the main jet. This ratio is written as the product of the ratio of the densities (fluid on the main fluid) and the ratio of the square of the speed of the actuator jets and the square of the speed of the main jet).
  • the main fluid is the same for all the experiments, while different fluids have been used for the actuators. These fluids differ mainly in their density (from the density of the largest to the lowest: CO2, Air, Air Helium mixture). It is observed that all the experimental points (whatever the flow rates and the fluids used) are aligned on a line. This shows that the physical parameter that controls the opening is the ratio of the specific pulses defined above.
  • the burner with separate injections 101 comprises a top row of oxygen injectors 112 in the form of jets and injectors of natural gas (fuel) 125 in the form of jets, all of the injectors being in the refractory mass 121 ( Figure 7C ).
  • the usually metallic portion 102 of the burner 101 is located on the right side of the Figure 7A and is extended by the tubes 107 and 109 of oxygen gas injection, on the one hand, 207 and 209 natural gas injection, on the other hand on the left of the Figure 7A .
  • the wall 109 is extended by the walls 113, inclined upwards, 114, horizontal and vertical 115 (in the figure), while a central volume 126 delimits a channel 127 first inclined upwards, horizontal then vertical (that is to say 90 ° relative to the gaseous flow channel 108 and opening therein through the opening 120).
  • the vertical portion of the channel 127 has a height L, defined above, to ensure the orthogonality of the jets 110 and 108 at 120 (of course, if we choose an angle of intersection of the jets different from 90 °, the channel 127 will have the desired inclination and its length L remaining within the limits provided above).
  • the metal part of the burner ends with a wall 123, vertical in this case, bordering the channel 127, metal part exposed to the heat radiation of the fireplace in use.
  • a protective element for example alumina, resistant to high temperatures, coming, for example, to fit on this metal end to protect it and having a opening equal to the opening 112 ( Figure 7C ).
  • the fuel supply system 204, 206, 203, 205 is similar to the oxidizer feed system described above with a main channel 207, an actuator channel 209 defining main fuel jets 208 and fuel actuators 210, all housed in a cylindrical opening 222 of the opening 221 (similar to 122 for the oxidant).
  • the ends 124 and 125 are similar to 123 and 112.
  • the same fuel actuator jet injection system is provided at the end of 207 and 209 as shown in FIG. Figure 7B , sized according to the characteristics of the fuel. In general, however, it will be preferable to provide only one jet injector jet on the fluid having the highest pulse (generally the oxidizer in the case of a burner), the jet thus deflected itself causing the deflection of the other jet outside the burner.
  • the highest pulse jet (or row of jets) will generally be disposed above the lower impulse jet, so that without the action of the jet actuator on the jet of highest impulse, the burner delivers a directed flame generally horizontally, whereas when the jet actuator (coming to act up and down on the main jet of higher momentum) acts on the main jet, it is directed, as explained above, downwards (progressively, according to the ratio of the pulses) and carries with it the second lower pulse jet (here the fuel) forming a flame which can thus pass from a horizontal position to an inclined position towards the load to be heated, under the burner flame.
  • the second lower pulse jet here the fuel
  • the actuator jet makes with the main jet an angle which is greater than zero.
  • the two channels leading these jets are fed most often by a co-axial feed system (parallel channels - see figure 7 ).
  • the invention will hereinafter be illustrated in the case of a burner useful for heating any load which may be a metal charge or any other charge which must be melted and / or brought to a high temperature and then maintained at that temperature.
  • a load which may be a metal charge or any other charge which must be melted and / or brought to a high temperature and then maintained at that temperature.
  • ci for example a charge of ferrous or non-ferrous metal, solid materials for the production of glass, for that of cement or on the contrary a charge which must be dried from a liquid bath.
  • this type of tool generally comprises a flame (usually subsonic) which allows to heat the metal, melt it, especially at the beginning of a merger.
  • This flame may be of variable direction by equipping each main jet (oxidizer, fuel, premix) or at least one main jet of a jet actuator which varies its direction and / or its opening, so as to move this flame on the load without requiring heavy mechanical means that change the direction of the burner body.
  • These tools are often also equipped with injection sprays of pulverized coal, usually injected with carrier gas in a lance.
  • the following examples relate to the control of the heat transfer by a burner according to the invention to a charge, for example a metal charge, in a process for melting a charge.
  • An aluminum smelting furnace is generally equipped with one or more burners on one or more of the side walls surrounding the furnace smelter, disposed above the waterline when the metal is fully melted (liquid ).
  • the axis of the flame, when it is horizontal, is located at a height of 10 and 100 cm from this waterline, preferably between 40 and 80 cm.
  • Burners according to the invention are used so that the flame incidence is variable.
  • Incidence is defined as the angle of the flame to the horizontal). When the incidence is zero, the flame is horizontal. When the incidence is non-zero, the flame is inclined below the horizontal and directed towards the bottom of the melting basin of the furnace.
  • the burners inject each jet of fluid into the furnace chamber, but this type of injector can be used only for the higher impulse fluid (oxidant or fuel) when it can interact with the one of the least impulse. to obtain the desired deviation of the flame, typically, the oxidant in the case of an air burner / gaseous fuel, or oxygen / gaseous fuel.
  • the direction of the flame is adjusted so that the latter has a non-zero incidence (axis of the flame between 5 ° and 75 °, preferably between 25 ° and 45 °). This adjustment considerably improves the thermal transfer of the burner and thus reduces the duration of the melting (as explained with the aid of FIG. figure 10 ).
  • the direction of the flame is adjusted to have a zero angle of incidence. The flame is therefore parallel to the waterline of the liquid metal. This setting makes it possible to continue transferring energy to the charge and to complete the melting of the metal or to refine it by limiting the heating of the already molten metal and consequently its oxidation by the flame or the products of combustion. .
  • the incidence of the flame is between 5 ° and 30 ° preferably between 10 ° and 25 °, to obtain a compromise between covering the furnace charge by the flame (projected area of the flame on the bath) and intensity of the heat transfer.
  • the figure 12 illustrates the extreme positions of the flame with respect to the load.
  • the figure 12a is a top view of an aluminum melting furnace equipped with two burners according to the invention producing two flames positioned above the metal bath.
  • the chimney of the oven allows the evacuation of the fumes produced by the flames.
  • the Figures 12b and 12c represent a side view of the same furnace, at the level of the flame.
  • the oven operator can vary the incidence between 0 ° to 45 ° and then return to 0 °.
  • the burner will be controlled with a control unit making it possible to periodically modulate the burner control ratio, that is to say the ratio of the pulses of the main and actuator jets and consequently the incidence of the flame on the bath.
  • the control signal of the control box may be sinusoidal, triangular, square, etc. with a variable frequency of 0.05 Hz to 100 Hz, preferably triangular at a frequency of 0.1 to 10 Hz.
  • the periodic variation of the position of the flame makes it possible to homogenize the transfer of heat inside the oven and thus to melt more quickly the solid elements.
  • Burners according to the invention are used so that the orientation of the flame in a horizontal plane can be modified on demand according to the control ratio of each burner as illustrated in FIG. figure 13 .
  • Each jet of fluid is injected into the furnace chamber by means of a burner according to the invention, but for jets located in the same horizontal plane or horizontal planes closely spaced from each other (from one to two jet diameters), we can only use these injectors for the peripheral jets when they can interact with the other jets to deviate.
  • the variation of the horizontal orientation can be done in both the left and right directions either by equipping each main jet with two lateral actuator jets, or by equipping each main main jet with a single jet actuator, capable of actuating the main jet. in the horizontal direction but in opposite directions to each other.
  • control ratio used above is defined as the ratio of the flows of the actuator jet and the main jet, knowing that the pulse of a jet of fluid can be controlled simply by the variation of the opening of the jet.
  • the figure 13 illustrates an example of horizontal displacement of a flame over a load; each main jet 130, 132 (oxidizer or fuel) is provided with an actuator jet 131, 133; on the figure 13a , the control ratio CR of the jet 130 is zero, ie no fluid is injected into the channel 131; the control ratio CR of the jet 132 is on the other hand positive, which means that since 133 acts from bottom to top on the figure 13a , the actuator jet 133 deflects the main jet 132 upwards in the figure, ie to the left relative to the axis X - X 'of the burner.
  • the control ratio CR of the jet 130 and the jet is positive, resulting in a derivation of the flame downwards in the figure (towards the right in a view from above), the main jet 132 and the jet actuator 133 having a ratio null control (no jet 133).
  • each burner can cover a larger portion of the charge favoring the homogeneity of the heat transfer and making it possible to limit the possible formation of hot spots if refractory materials are in the bath (for example residues based on alumina, recycled or in course of formation by oxidation of the metal being melted), and to promote overall heat transfer to accelerate the constant power melting process, or reduce energy consumption constant melting time.
  • refractory materials for example residues based on alumina, recycled or in course of formation by oxidation of the metal being melted
  • Example 3 flame with variable incidence on the load and which sweeps the load laterally.
  • All primary techniques for reducing nitrogen oxide emissions from burners or industrial fireplaces use the local properties of fluid or flame flows to limit their formation. In particular they aim to reduce the temperature or the concentrations of the reagents (fuel, oxygen) or the residence time of the reactants in the flame and / or in the products of combustion.
  • One of these techniques involves driving enough flue gas into the reagents or into the flame to lower the temperatures, the concentration of reagents or reduce the residence time.
  • the burner is dimensioned so as to obtain fuel jets and / or oxidant at high speed (high pulse) and sufficiently distant to obtain the maximum rate of entrainment or recirculation of flue gas compatible with good stabilization of the flame.
  • the stabilization limit is detected at the occurrence of unburned in combustion products such as carbon monoxide for hydrocarbons. Under certain conditions it is possible to obtain a "flameless" combustion regime that is particularly favorable to the reduction of emissions.
  • the limitation of this technique and the combustion technologies that use it is that the flue gas entrainment rate is set by the burner dimensions and the operating conditions. As a consequence, the emissions performance can deteriorate very significantly as soon as these conditions are removed, but also when fuel is changed, or when the furnace or furnace-specific flows contribute significantly to the emissions. properties of the flames.
  • the invention makes it possible to adapt in operation the properties of the flames and in particular the rate of recirculation of burnt gases, which makes it possible to minimize in all circumstances emissions of pollutants and ultimately optimize the performance of burners.
  • Example 6 premix burner consisting of an injector placed in a fireplace.
  • Actuator jets as described above are used to modify in operation the opening angle of the main fluid jet (or several jets).
  • the main jet is a gaseous premix of fuel and oxidizer.
  • the opening of the jet measures the level of entrainment of the ambient environment by the latter, it can be measured by the angle between the axis of the jet and the line tangent to the boundary between the jet and the ambient environment. (This boundary can be defined as the place in the jet where the concentration of the injected fluid becomes zero).
  • the opening of the jet is controlled by the ratio between the flow of the jet actuator and the total flow of the resulting jet.
  • this control ratio is zero, a level of emission N1 is measured ( figure 15 ).
  • This control ratio is actually the ratio of jet pulses as explained above.
  • the control parameter is then increased so as to increase the entrainment of burnt gases in the jet and thus dilute the injected fuel mixture. This dilution will lead to, on the one hand, reducing the temperature and, on the other hand, the concentration of the reagents in the flame. NOx emissions will therefore decrease until reaching an N2 level ( figure 15 ). If the value of the control parameter is further increased, the temperature and the concentrations of the reactants become too low to ensure a good stabilization of the flame: unburnt appear in the combustion products. The emissions of nitrogen oxides are then at a level N3 and the emissions of unburnt at a level I3 too high.
  • the control parameter is then reduced until the optimal level of the emissions N0 and I0 (intersection of the NOx and unbroken curves on the figure 15 ).
  • This optimum can be obtained manually (passive control) or preferably by a control device active.
  • This device integrates sensors for the measurement of emissions of nitrogen oxides and unburnt, an automat using the control logic explained above and the control devices of the flows of the main jet and the jet (s) actuator (s) at least one injector.
  • the controller will determine the value of the control parameter that minimizes emissions of nitrogen oxides and unburnt.
  • the active control becomes indispensable as soon as the number of parameters to be optimized is greater than or equal to two. For example one can at the same time want to minimize pollutant emissions by increasing the rate of dilution of the flame by the flue gases and maximize the transfer to the load by inclination of the flame to the load.
  • control can be exercised indifferently on the fuel, the oxidant or both in a manner analogous to Example 5.
  • the effects of opening (entrainment of the ambient environment) and deflection of the jets (divergent fuel and oxidant jet) will be combined, in particular to increase the impact of the dilution of the flame and to maximize the reduction of emissions.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion Of Fluid Fuel (AREA)
  • Gas Burners (AREA)
  • Pre-Mixing And Non-Premixing Gas Burner (AREA)

Claims (21)

  1. Brenner, der Folgendes umfasst:
    - eine Passage (10, 310, 410, 308, 608), um einen Primäroxidationsmittelstrahl oder einen Primärkraftstoffstrahl oder einen Primäroxidationsmittel-Kraftstoff-Vorgemischstrahl zu einer Hauptausgangsöffnung (11, 311, 611) zuzuführen,
    - mindestens eine Sekundärkanalisation (21, 321, 322, 323, 324, 421, 422, 423, 424, 622, 624) zum Einspritzen eines Sekundärstrahls und die in Bezug auf die Passage (10, 310, 410, 608) derart positioniert ist, dass an der Wechselwirkungsstelle zwischen dem entsprechenden Sekundärstrahl und dem Primärstrahl der Winkel θ zwischen der Achse des entsprechenden Sekundärstrahls und der Ebene senkrecht zu der Achse des Primärstahls größer oder gleich 0° und kleiner als 90° ist, vorzugsweise von 0° bis 80°, und noch bevorzugter auch von 0° bis 45°,
    wobei der Brenner Impulsreguliermittel jedes entsprechenden Sekundärstrahls umfasst und es ermoglicht, die Richtung und/oder die Öffnung der Flamme (1) variieren zu lassen, indem der Impuls mindestens eines entsprechenden Sekundärstrahls geändert wird,
    dadurch gekennzeichnet, dass die mindestens eine Sekundärkanalisation (21, 321, 322, 323, 324, 421, 422, 423, 424, 622, 624) durch eine Sekundäröffnung (31, 331, 332, 333, 334, 431, 432, 433, 434, 632, 634), die stromaufwärts der Hauptausgangsöffnung (11, 311, 611) liegt, in der Passage (10, 310, 410, 608) ausmündet, wobei die mindestens eine Sekundäröffnung (31, 331, 332, 333, 334, 431, 432, 433, 434, 632, 634) von der Hauptausgangsöffnung (11, 311, 611) um eine Entfernung L beabstandet ist, die kleiner oder gleich zehn Mal der Quadratwurzel des Querschnitts s der Hauptausgangsöffnung (11, 311, 611) ist, vorzugsweise L
    Figure imgb0001
    5 * s ,
    Figure imgb0002
    noch bevorzugt L 3 * s .
    Figure imgb0003
  2. Brenner nach Anspruch 1, wobei die Reguliermittel das Verhältnis zwischen dem Impuls jedes entsprechenden Sekundärstrahls und dem Impuls des Hauptstrahls steuern.
  3. Brenner nach einem der vorhergehenden Ansprüche, der mindestens eine Sekundärkanalisation (21, 321, 322, 323, 324, 622, 624) umfasst, die in Bezug zu der Passage (10, 310, 608) derart positioniert ist, dass sich die Achsen des Primärstrahls und des Sekundärstrahls im Bereich der entsprechenden Sekundäröffnung (31, 331, 332, 333, 334, 632, 634) schneiden oder quasi schneiden, um den Winkel der Flamme am Ausgang des Brenners in Bezug zu der Achse des Primärstrahls stromaufwärts der entsprechenden Sekundäröffnung variieren lassen zu können.
  4. Brenner nach Anspruch 3, der mindestens zwei Sekundärkanalisationen (321, 322, 323, 324, 622, 624) umfasst, die in Bezug zu der Passage (310, 608) derart positioniert sind, dass die zwei entsprechenden Sekundäröffnungen (331, 332, 333, 334, 632, 634) in derselben Ebene senkrecht zu der Achse des Primärstrahls liegen, und dass im Bereich dieser zwei entsprechenden Sekundäröffnungen (331, 332, 333, 334, 632, 634) die Achsen der entsprechenden Sekundärstrahlen die Achse des Primärfluidstrahls schneiden oder quasi schneiden.
  5. Brenner nach Anspruch 4, wobei die zwei entsprechenden Sekundäröffnungen (331, 332, 333, 334, 632, 634) zu der Achse des Primärstrahls im Bereich der zwei Sekundäröffnungen (331, 332, 333, 334, 632, 634) komplanar sind und zu beiden Seiten dieser Achse des Primärstrahls liegen.
  6. Brenner nach Anspruch 4, wobei die Ebene, die durch die Achse des Primärstrahls im Bereich der zwei entsprechenden Sekundäröffnungen (331, 332, 333, 334, 632, 634) und eine der zwei entsprechenden Sekundäröffnungen (331, 332, 333, 334, 632, 634) definiert ist, und der Ebene, die durch die Achse des Primärstrahls und der anderen der zwei entsprechenden Sekundäröffnung (331, 332, 333, 334, 632, 634) definiert ist, senkrecht zu einander stehen.
  7. Brenner nach einem der Ansprüche 4 bis 6, der mindestens vier Sekundärkanalisationen (321, 322, 323, 324) umfasst, die in Bezug zu der Passage (310, 410) derart positioniert sind, dass die vier entsprechenden Sekundäröffnungen (331, 332, 333, 334) in derselben Ebene senkrecht zu der Achse des Primärstrahls liegen, und dass im Bereich dieser vier Sekundäröffnungen (331, 332, 333, 334) die Achsen der entsprechenden Sekundärstrahlen die Achse des Primärstrahls schneiden oder quasi schneiden, wobei zwei dieser entsprechenden Sekundäröffnungen (331, 332, 333, 334) in einer erster Ebene mit der Achse des Primärstrahls komplanar sind und zu beiden Seiten dieser Achse liegen, wobei die zwei anderen entsprechenden Sekundäröffnungen (331, 332, 333, 334) in einer zweiter Ebene mit der Achse des Primärstrahls komplanar sind und zu beiden Seiten dieser Achse liegen.
  8. Brenner nach einem der vorhergehenden Ansprüche, wobei mindestens eine Sekundärkanalisation (421, 422, 423, 424, 624) in Bezug zu der Passage (410) derart positioniert ist, dass im Bereich der entsprechenden Sekundäröffnung (431, 432, 433, 434) die entsprechende Achse des Sekundärfluidstrahls mit der Achse des Primärfluidstrahls nicht im Wesentlichen komplanar ist, um eine Drehung des resultierender Fluidstrahls um seine Achse zu erzeugen, aufrechtzuerhalten oder zu verstärken und dadurch die Öffnung der Flamme am Ausgang des Brenners variieren zu lassen.
  9. Brenner nach Anspruch 8, der mindestens zwei Sekundärkanalisationen (421, 422, 423, 424) umfasst, die in Bezug zu der Passage (410) derart positioniert sind, dass die Achsen der entsprechenden Sekundärstrahlen mit der Achse des Primärstrahls nicht im Wesentlichen komplanar sind, und dass die entsprechenden Sekundärstrahlen mit einer und derselber Rotationsrichtung um die Achse des Primärstrahls ausgerichtet sind.
  10. Brenner nach Anspruch 9, wobei die zwei entsprechenden Sekundäröffnungen (431, 432, 433, 434) zu beiden Seiten der Achse des Primärstrahls liegen.
  11. Brenner nach einem der vorhergehenden Ansprüche, wobei mindestens eine Sekundärkanalisation (21) in Bezug zu der Passage (10) derart positioniert ist, dass in dem Bereich der entsprechenden Sekundäröffnung (31) die Sekundärkanalisation (21) eine Dicke e und eine Höhe ℓ aufweist, wobei die Höhe ℓ größer oder gleich 0,5 Mal der Dicke e, vorzugsweise zwischen 0,5 x e und 5 x e liegt.
  12. Brenner nach einem der vorhergehenden Ansprüche, der Mittel umfasst, um das Verhältnis der Impulse des Primärfluidstrahls und des Sekundärfluidstrahls zu steuern.
  13. Brenner nach einem der vorhergehenden Ansprüche, der einen Werkstoffblock (5, 605) umfasst, in dem mindestens ein Teil der Passage (10, 608) liegt, wobei die Hauptöffnung (11, 611) auf einer der Seiten oder Oberflächen (6) des Blocks (5, 605) liegt.
  14. Brenner nach einem der vorhergehenden Ansprüche, der Mittel zum Steuern der Impulse des Primär- und/oder Sekundärstrahls umfasst.
  15. Brenner nach einem der vorhergehenden Ansprüche, der einen Brennermaul (610) umfasst, der an dem Ende der Passage (608) angeordnet ist, und mindestens eine Sekundärkanalisation (622, 624), die durch eine Sekundäröffnung (3632, 634), die in dem Brennermaul liegt, in der Passage (608) mündet.
  16. Verfahren zum Erhitzen einer Charge mittels einer Flamme, wobei die Flamme erzeugt wird, indem ein Brenner nach einem der vorhergehenden Ansprüche verwendet wird.
  17. Verfahren nach Anspruch 16, wobei man die Richtung und/oder die Öffnung der Flamme variieren lässt, indem man einen Primärstrahl mit mindestens einem Sekundärstrahl in Wechselwirkung treten lässt.
  18. Verfahren nach Anspruch 17, wobei der Primärstrahl ein Strahl ist, der Oxidationsmittel oder Kraftstoff oder ein Vorgemisch aus Oxidationsmittel und Brennstoff enthält.
  19. Verfahren nach einem der Ansprüche 16 bis 18, wobei man die Richtung der Flamme variieren lässt, um mindestens einen Teil der Oberfläche der Charge zu überstreichen.
  20. Verfahren nach Anspruch 19, wobei man die Richtung der Flamme in mindestens zwei schneidenden Ebenen variieren lässt, um mindestens einen Teil der Oberfläche der Charge zu überstreichen.
  21. Verfahren nach einem der Ansprüche 16 bis 20, wobei man in einer ersten Phase die Flamme in Richtung der Charge lenkt, und man in einer zweiten Phase die Flamme im Wesentlichen parallel zu der Charge lenkt.
EP07823552.0A 2006-07-06 2007-07-05 Brenner mit einstellbarer richtung und/oder öffnung der flamme und dessen verwendung Not-in-force EP2041492B1 (de)

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PCT/FR2007/051598 WO2008003908A2 (fr) 2006-07-06 2007-07-05 Brûleur à flamme à direction et/ou ouverture variable et procédé de mise en oeuvre

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AUPN156295A0 (en) * 1995-03-07 1995-03-30 Luminis Pty Limited Variable flame precessing jet nozzle
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US5772422A (en) * 1996-08-27 1998-06-30 Pvi Industries, Inc. Burner array for water heating apparatus
JP4242247B2 (ja) * 2003-10-07 2009-03-25 大陽日酸株式会社 バーナー又はランスのノズル構造及び金属の溶解・精錬方法
ITMI20050241A1 (it) * 2005-02-18 2006-08-19 Techint Spa Iniettore multifunzione e relativo procedimento di combustione per trattamento metallurgico in un forno ad arco elettrico

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ES2604078T3 (es) 2017-03-02
EP2041492A2 (de) 2009-04-01
CN101484752B (zh) 2012-12-12
JP5221532B2 (ja) 2013-06-26
PL2041492T3 (pl) 2017-07-31
CN101484752A (zh) 2009-07-15
WO2008003908A3 (fr) 2008-05-02
FR2903479A1 (fr) 2008-01-11
JP2009543012A (ja) 2009-12-03
RU2433343C2 (ru) 2011-11-10
RU2009103903A (ru) 2010-08-20
WO2008003908A2 (fr) 2008-01-10
BRPI0714153A2 (pt) 2012-12-25
US20100068666A1 (en) 2010-03-18

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