[go: up one dir, main page]

EP1269076B1 - Procede et appareil pour un reacteur a foyer catalytique - Google Patents

Procede et appareil pour un reacteur a foyer catalytique Download PDF

Info

Publication number
EP1269076B1
EP1269076B1 EP00921557A EP00921557A EP1269076B1 EP 1269076 B1 EP1269076 B1 EP 1269076B1 EP 00921557 A EP00921557 A EP 00921557A EP 00921557 A EP00921557 A EP 00921557A EP 1269076 B1 EP1269076 B1 EP 1269076B1
Authority
EP
European Patent Office
Prior art keywords
conduits
retainer
conduit
catalytic
reactor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00921557A
Other languages
German (de)
English (en)
Other versions
EP1269076A4 (fr
EP1269076A1 (fr
Inventor
Lance L. Smith
Shahrokh Etemad
Md. Hasan Ul Karim
Marco J. Castaldi
William C. Pfefferle
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Precision Combustion Inc
Original Assignee
Precision Combustion Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Precision Combustion Inc filed Critical Precision Combustion Inc
Publication of EP1269076A1 publication Critical patent/EP1269076A1/fr
Publication of EP1269076A4 publication Critical patent/EP1269076A4/fr
Application granted granted Critical
Publication of EP1269076B1 publication Critical patent/EP1269076B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C13/00—Apparatus in which combustion takes place in the presence of catalytic material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23M—CASINGS, LININGS, WALLS OR DOORS SPECIALLY ADAPTED FOR COMBUSTION CHAMBERS, e.g. FIREBRIDGES; DEVICES FOR DEFLECTING AIR, FLAMES OR COMBUSTION PRODUCTS IN COMBUSTION CHAMBERS; SAFETY ARRANGEMENTS SPECIALLY ADAPTED FOR COMBUSTION APPARATUS; DETAILS OF COMBUSTION CHAMBERS, NOT OTHERWISE PROVIDED FOR
    • F23M5/00—Casings; Linings; Walls
    • F23M5/08—Cooling thereof; Tube walls
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23D—BURNERS
    • F23D2214/00—Cooling
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23D—BURNERS
    • F23D2900/00—Special features of, or arrangements for burners using fluid fuels or solid fuels suspended in a carrier gas
    • F23D2900/00001—Special features of, or arrangements for burners using fluid fuels or solid fuels suspended in a carrier gas local catalytic coatings applied to burner surfaces

Definitions

  • the present invention relates to catalytic reactor design. More specifically, the invention is a catalytic reactor for converting a fuel/oxidant mixture into a fuel/oxidant/product mixture and heat.
  • the reactor employs an exothermic catalytic reaction channel cooled by numerous cooling channels, where the cooling fluid is a portion of the ultimate fuel/oxidant/product mixture.
  • a further refinement in the invention incorporates geometric changes in the exothermic and/or cooling portions of the reactor to provide streamwise variation of the velocity of the fluids in the reactor.
  • the reactors are typified by exothermic reactions within the catalytic portion of the reactor and a cooling means to control the temperature within the catalytic portion to avoid a material failure, either of the substrate or the catalyst. Cooling in these reactors can be accomplished by a number of means, including placing the catalyst in a backside-cooled relationship with the cooling agent.
  • a backside-cooling arrangement is particularly suitable for catalytic reactions that are both rapid and highly exothermic, such as catalytic combustion.
  • the catalyst substrate typically a metal foil
  • the catalyst substrate is coated with an oxidation catalyst on only one side, the opposite side (or backside) remaining free of oxidation catalyst.
  • the substrate is shaped and assembled, before or after catalyst coating, to create separate channels for exothermic reaction (in the channels coated with oxidation catalyst) or for cooling (in the channels free of oxidation catalyst). Fluid passing through the cooling channels removes a portion of the heat generated in the exothermic reaction channels.
  • the '250 patent further refines the structure claimed by the '824 and '489 patents.
  • Dalla Betta et al. teach a structure in which periodic alterations in channel shape provide different wall heat transfer rates in the catalytic channels and non-catalytic channels.
  • Young et al. namely a multitude of catalytic channels and adjacent non-catalytic channels, is retained.
  • the prior art backside-cooled catalytic reactors include a multitude of catalytic channels, where each individual catalytic channel is in essence a separate catalytic reactor.
  • variations in fuel/air ratio from channel to channel can lead to different degrees of combustion and heat release in different channels.
  • variations in inlet temperature from channel to channel can also lead to variations in combustion behavior in different channels.
  • Rate of reaction, catalyst light-off length, and maximum gas or surface temperature can all be affected by the temperature and fuel/air ratio at a channel inlet.
  • manufacturing tolerances may result in unequal physical properties of different channels. Properties which may vary include channel size, wall thickness, catalyst or washcoat thickness, and catalyst loading; each of these may affect combustion behavior.
  • multiple catalytic channels can produce widely varying degrees of catalytic combustion.
  • US Patent 4, 305, 910 to Kudo et al. describes a catalytic reactor for reducing nitrogen oxide (NO x ) contained in exhaust gas under the presence of ammonia, wherein tubular catalyst units each being a ring shape in cross-section are disposed in spaced apart relationship from one another in the cross-section of the flow path of the exhaust gas in a manner that tubular axes thereof are in parallel with the direction of gas flow within a reaction vessel through which the exhaust gas containing nitrogen oxide (NO x ) and ammonia flows, said catalyst units each being secured to the interior of the reaction vessel at least as two points in the longitudinal direction by support means.
  • NO x nitrogen oxide
  • the un-partitioned exothermic catalytic reaction channel allows for continual mixing of the fuel/oxidant stream within the channel leading to a more uniform combustion and a wider operating range.
  • the structure of the present invention is more flexible, facilitating cross-stream area changes in the streamwise or longitudinal direction, since there is no constraint that walls contact each other to form multiple catalytic channels.
  • the invention can be used to vary the bulk fluid properties in the streamwise or longitudinal direction via cross-stream area changes.
  • it may be desirable to reduce the velocity of the fuel/air mixture after it has entered the exothermic catalytic reaction channel, to provide greater residence time for reaction within the reactor, while maintaining sufficient velocity at the reactor inlet to prevent flashback to the fuel/oxidant mixture upstream of the reactor.
  • the present invention is a catalytic firebox reactor, is a catalytic reactor employing an un-partitioned exothermic catalytic reaction channel and multiple cooling conduits passing through the exothermic catalytic reaction channel.
  • An oxidation catalyst is deposited on the exterior surfaces of the conduits within the exothermic catalytic reaction channel. This placement of the catalyst allows the oxidation catalyst to be backside cooled by any fluid passing through the cooling conduits.
  • Backside cooling means that at each location where an oxidation catalyst is deposited on one surface of a wall no oxidation catalyst is deposited on an adjacent or opposite surface in contact with the cooling fluid, and a portion of the heat generated by reaction on the oxidation catalyst is conducted through the substrate to the adjacent or opposite surface that is in direct contact with the cooling fluid.
  • the catalytic firebox reactor can be made in numerous configurations with the following common elements.
  • a casing forms the outer boundary, which can be of any shape.
  • the reactor casing can be a single fabricated component, or can consist of two or more components (such as a mixing duct and a conduit support duct) joined together.
  • Two or more conduits are placed within the casing such that one fluid stream can traverse an un-partitioned channel, the exothermic catalytic reaction channel, defined by the interior surface of the casing and the exterior surfaces of the conduits, and a number of separate fluid streams can traverse the passages defined by the interior surfaces of the conduits, without mixing occurring between fluid in the exothermic catalytic reaction channel and fluid in the conduits' interior passages.
  • a heat transfer relationship exists between the fluid in the exothermic catalytic reaction channel and the fluids in the conduits' interior passages.
  • the exothermic catalytic reaction channel is the region between the conduits exterior surfaces and the reactor casing's interior surface, beginning immediately downstream of the most downstream conduit inlet and ending immediately upstream of the most upstream conduit outlet (note that the most downstream conduit inlet is upstream of the most upstream conduit outlet).
  • This region forms an un-partitioned channel because an intentional gap is made between adjacent conduits for some portion of the conduits' length, within the exothermic catalytic reaction channel.
  • un-partitioned means that any two points within the channel can be connected by a path contained entirely within the channel.
  • upstream and downstream refer to the location of imaginary cross-stream surfaces, so that points which are not on the same streamline can have a definite upstream-downstream relationship.
  • Cross-stream means perpendicular to the flow, so that streamlines of the flow always intersect a cross-stream surface perpendicularly.
  • a first point is said to be upstream of a second point if the cross-stream surface on which the first point lies is upstream of the cross-stream surface on which the second point lies.
  • the intentional gaps between adjacent conduits allow the exothermically catalyzed fluid to mix as the fluid catalytically reacts, so that non-uniformities in fluid velocity, fluid composition, and fluid temperature are ameliorated before the fluid exits the reactor.
  • Incidental leakage of the exothermically catalyzed fluid between adjacent conduits is not considered an intentional gap. Rather, the intentional gaps must be of sufficient size that fluid may freely pass through the gaps. Specifically, this means that the sum of the flow areas through all of the gaps within the exothermic catalytic reaction channel must be greater than the channel's minimum cross-stream flow area.
  • the cross-stream flow area of the exothermic catalytic channel is the area over which exothermically catalyzed fluid passes through an imaginary cross-stream surface within the channel.
  • the flow area is defined as the minimum area within the exothermic catalytic reaction channel of an imaginary surface which passes through the axial (streamwise) centerlines of both conduits and which extends between a straight line connecting the two conduit inlets and a straight line connecting the two conduit outlets.
  • Oxidation catalyst is deposited on at least a portion of the conduits' exterior surfaces within the exothermic catalytic reaction channel.
  • the oxidation catalyst provides the exothermic reaction surface which supports the exothermic oxidation of fuel within the exothermic catalytic reaction channel.
  • Catalyst coating may be applied to all of the conduits, or to only some of the conduits (leaving some of the conduits un-coated). In general, it is preferred that no oxidation catalyst is applied upstream of the most downstream conduit inlet, so that catalyzed fluid cannot enter any of the cooling conduits.
  • the conduits can be made in numerous configurations (cylindrical, fluted, externally finned, internally finned, internally partitioned, of round, lobed, polygonal, elliptical, or other cross-sectional shapes, straight or twisted, and so on), and can be arranged in numerous configurations within the casing (square-packed, close-packed, braided or spiraled, crisscrossed, and so on) using conduits of equal or unequal cross-sectional size, and of equal or unequal length.
  • a conduit may contain a single cooling passage, as in a simple tube for example, or a conduit may contain more than one cooling passage.
  • two parallel straight tubes may be joined to form a single conduit containing two cooling passages.
  • a divider may; be inserted in a single tube to create a conduit containing two cooling passages.
  • Three or more cooling passages may also be formed in a single conduit, if desired. In all configurations, however, oxidation catalyst is applied only to the conduits' exterior surfaces, and the conduits must be configured with an intentional gap between adjacent conduits such that a single exothermic catalytic reaction channel is formed.
  • the present invention is also a method for using a backside-cooled catalyst structure, wherein the velocities of the exothermically catalyzed stream and the cooling stream may be separately varied as the streams pass through the reactor, and in particular where the velocity of the exothermically catalyzed stream is reduced, after the stream enters the exothermic catalytic reaction channel, by a streamwise increase in the cross-sectional (cross-stream) area of the exothermic catalytic reaction channel.
  • the term "streamwise" means in the direction of the flow.
  • the catalytic firebox structure can be configured to accomplish this variation of velocity by a streamwise reduction in the cross-stream area of the cooling conduits, resulting in a streamwise increase in the cross-stream area of the exothermic catalytic reaction channel, if the wall thickness between the cooling conduits and the exothermic catalytic reaction channel remains unchanged, and if the total cross-stream area of the reactor (including both the cooling conduits and the exothermic catalytic reaction channel) remains unchanged.
  • Other means for reducing the velocity of the exothermically catalyzed stream area also possible, such as limiting the entrance flow area to the exothermic catalytic reaction channel by a baffle, plate, or other structure.
  • the cooling fluid and the exothermically catalyzed fluid comprise portions of an ultimate combustion mixture.
  • a fuel/oxidant mixture passes through the exothermic catalytic reaction channel it catalytically reacts.
  • the heat of reaction is added to both the fluid in the exothermic catalytic reaction channel and the fluid passing through the cooling conduits.
  • the fluids are allowed to mix such that a single combined flow is created.
  • the catalytic firebox reactor is a structure comprised of an exothermic catalytic reaction channel 60 penetrated by multiple cooling conduits 20 for backside cooling of oxidation catalyst 50 supporting the reaction within the channel.
  • a portion of a fuel/oxidant mixture 80, 80a enters the exothermic catalytic reaction channel 60 and is exothermically catalytically reacted on oxidation catalyst 50, while simultaneously a portion the fuel/oxidant mixture 80, 80b, enters the multiple cooling conduits 20 and cools the catalyst 50.
  • the exothermically catalyzed fluid 80a then exits the exothermic catalytic reaction channel 60 and mixes with the cooling fluid 80b exiting the multiple cooling conduits, creating a heated combustible fuel/oxidant/product mixture.
  • FIG. 1 depicts a catalytic firebox reactor employing an exothermic catalytic reaction channel with an interstitial entrance and exit strategy.
  • the reactor is comprised of a casing 10 into which conduits 20 are placed.
  • An oxidation catalyst 50 is deposited on the exterior surfaces of the conduits 20 within the exothermic catalytic reaction channel 60.
  • the conduits are expanded at their inlets and outlets.
  • the reactor is fabricated from a square-packed arrangement of parallel, equal-length, cylindrically-shaped conduits 20.
  • the expanded sections 15 perform the dual function of creating a single un-partitioned exothermic catalytic reaction channel, by providing a gap between the conduits, and creating an entrance into (and exit from) the exothermic catalytic reaction channel by creating a series of interstices between adjacent expanded end-sections.
  • a similar configuration could be created by expanding the conduits near, but not at, their inlets and outlets (an example of this is shown later, in Figure 8 ).
  • a single fuel/air mixture stream enters the casing and is split between the exothermic catalytic reaction channel and the multiple conduits' cooling passages. At the exit of the reactor the catalyzed stream and the cooling streams mix to create a single heated, partially reacted, fuel/air/product mixture stream.
  • the expanded sections 15 at the ends of each conduit are cylindrical (round), and are concentric with the conduit centerlines.
  • Other cross-sectional shapes of the expanded sections are also possible, including ellipses, squares, hexagons, octagons, lobed shapes ("clover-leaf”), and so on.
  • the term "expanded" means that at some axial location the maximum diameter of the conduit is greater than the maximum diameter of the conduit at other axial locations.
  • Figure 2 shows another embodiment of a catalytic firebox reactor employing expanded conduit end-sections 15 in conjunction with a retainer strategy.
  • the conduits 20 are expanded at the inlets and outlets and positioned within casing 10.
  • the expanded sections position the conduits 20 laterally within the casing 10.
  • a first retainer 33 is positioned at or near the conduit inlets and a second retainer 34 is positioned at or near the conduit outlets.
  • the retainers, 33 and 34 longitudinally position conduits 20 within the casing.
  • Figure 3 is a cross-section of this reactor taken immediately downstream of the conduit entrances, looking upstream, showing that the expanded end-sections position the conduits 20 laterally within the casing 10 and provide interstices for fluid to enter the exothermic catalytic reaction channel.
  • Figure 4 is a cross-section of this reactor taken in the middle looking upstream and shows that the expanded sections create a single un-partitioned exothermic catalytic reaction channel by providing gaps between the conduits 20.
  • the retainers 33 and 34 are shown as honeycombs.
  • the cell size of the honeycomb is no larger than the expanded conduit ends, so that the conduits are not able to pass through the honeycomb cells.
  • oxidation catalyst 50 is deposited on the exterior surfaces of the conduits 20 within the exothermic catalytic reaction channel 60.
  • Figure 5 shows another configuration of the reactor employing a retainer strategy.
  • the conduits 20 are inserted in a first retainer 36 and a second retainer 37, and may or may not have expanded end-sections.
  • the conduits may be attached to the first retainer 36, the second retainer 37, or both, by, for example, welding or brazing or press fit. If attachment at only one end is preferred, the conduits may slide freely through one of the retainers; for example, the conduits may be welded to the first retainer 36, but may slide freely through the second retainer 37.
  • the retainers in Figure 5 have passages that are open to the passage of fluid, as shown in Figure 6 .
  • Passages 70a permit fluid to enter the exothermic catalytic reaction channel 60 while passages 70b (not shown) permit the fluid to exit.
  • Passages 71a permit fluid to enter the conduits' 20 while passages 71b (not shown) permit the fluid to exit.
  • Oxidation catalyst 50 is deposited on the exterior surfaces of conduits 20 within the exothermic catalytic reaction channel 60.
  • a variation of the embodiment shown in Figure 5 may incorporate only one retainer. In this case, the conduits pass through a single retainer 36, and may be attached to the retainer by, for example, welding or brazing or press fit.
  • Figure 7 shows a similar configuration to that shown in Figure 5 , but shows a different method of retaining the conduits.
  • the conduits 20 are inserted through a first retainer 36 and a second retainer 37, but are not attached to the retainers. Instead, each conduit passes through the retainers and is expanded at each end, to a size which does not permit the expanded conduit ends 15 to pass through the retainers. Thus, no attachment to the retainers is required, and the conduits may slide freely through the retainers until an expanded end contacts a retainer.
  • the retainers are attached to the reactor casing 10.
  • the retainers in Figure 7 have passage 70a and 70b that permit fluid to enter and exit the exothermic catalytic reaction channel 60, respectively.
  • Oxidation catalyst 50 is deposited on the exterior surfaces of conduits 20 within the exothermic catalytic reaction channel 60.
  • FIG. 8 A close-packed configuration of expanded-end conduits is shown in Figure 8 .
  • the conduits 20 are arranged within casing 10 with the conduit centerlines lying on an imaginary grid consisting of adjacent equal-size equilateral triangles, so that each conduit is in direct contact with those adjacent at the expanded end-sections.
  • the imaginary grid lines in this close-packed case consist of three sets of parallel, equally-spaced lines, each set of lines being oriented at a 60-degree angle from each other set of lines.
  • the conduits are attached to one another forming a bundle and conduits adjacent to the casing are attached to the casing by, for example, welding or brazing.
  • Oxidation catalyst 50 is deposited on the exterior surfaces of conduits 20 within the exothermic catalytic reaction channel 60.
  • Figure 9 illustrates another close-packed configuration of conduits 20.
  • the expanded conduit sections 75 are located near, but not at, the tube ends.
  • the conduits are supported and located laterally in the same manner as in Figure 8 , but the inlet face to the reactor differs between the two cases.
  • the ratio of the inlet area of the conduits 20 to the total reactor cross-stream area (defined bv the casing 10 size) is greater in Figure 8 than in Figure 9 .
  • the conduits are attached to one another at their expanded sections, and conduits adjacent to the casing are attached to the casing at their expanded sections, by for example welding or brazing.
  • Oxidation catalyst 50 is deposited on the exterior surfaces of conduits 20 within the exothermic catalytic reaction channel 60.
  • the effective areas are in part determined by the cross-stream area at the entrance to a passage or channel.
  • a greater percentage of the flow will enter the exothermic catalytic reaction channel in the configuration of Figure 1 (square-packed) than in the configuration of Figure 8 (close-packed), and a greater percentage of flow will enter the exothermic catalytic reaction channel in the configuration of Figure 9 (expanded near, but not at, the conduit ends) than in the configuration of Figure 8 (expanded at the conduit ends).
  • the invention requires that the fluid exiting the exothermic catalytic reaction channel exit and the fluid exiting the conduit outlets must come into contact to permit some degree of mixing to form the ultimate combustion mixture.
  • the exothermic catalytic reaction channel exit and the conduit outlets must be proximately located. Proximately located means that the exits are spatially located to permit the fluids exiting the exit and the outlets to come in contact so some degree of mixing is possible prior to ultimate combustion.
  • Figures 1, 2 , 5 , 8 and 9 show the closest possible stream wise proximate locations of the exothermic catalytic reaction channel exit and the conduit outlets, occurring essentially at the same streamwise location.
  • Figure 7 shows a configuration where the conduit outlets are downstream of the exothermic catalytic reaction channel.
  • Figures 1 through 9 illustrate several strategies for retaining the conduits 20 within casing 10.
  • the invention does not require symmetry in securing the upstream and downstream ends of the conduits and the different securing structures illustrated could be combined in a single embodiment.
  • the conduits 20 could be secured at the upstream end by a retaining structure and at the downstream end by an expanded conduit structure.
  • the casing and the conduits may operate at different temperatures, resulting in different amounts of thermal expansion.
  • clearance may be provided between the conduits and the upstream or downstream retainers, to allow for thermal growth of the conduits.
  • the conduits may be secured (by welding, for example) to each other and to the casing only at one end, as for example at the inlet or upstream end, with the other end free to move longitudinally so that differential thermal growth of the conduits may be accommodated. If a clearance is allowed between the conduits and the retainer(s), or if differential thermal growth between adjacent conduits is expected, the conduits' expanded sections (if employed) should be of sufficient axial length that lateral support and positioning of the conduits is provided even when adjacent tubes move in opposite axial directions to the maximum extent allowed by the clearance space or the expected difference in thermal growth.
  • the expanded sections need not provide lateral support to the conduits. In this case, it may also be advantageous to allow the conduits to slide freely through at least one of the retainers, to allow for thermal expansion of the conduits.
  • Conduits 20 can be fabricated from metal, preferably a high-temperature-tolerant alloy suitable for the application, which provides good heat transfer from the oxidation catalyst 50 to the cooling fluid contacting the interior surface of conduits 20.
  • Conduits 20 may have any wall thickness. Generally, thinner walls will be weaker and less resistant to long-term oxidation, while thicker walls will result in increased pressure drop through the reactor.
  • the preferred wall thickness is between 0.05 mm and 2 mm, with wall thicknesses between 0.1 mm and 1 mm being most preferred. If expanded sections are employed minor variations in wall thickness are acceptable.
  • Casing 10 is also fabricated from high-temperature tolerant materials. Wall thickness is based upon the application.
  • Oxidation catalyst 50 is applied to the exterior of conduits 20 within the exothermic catalytic reaction channel. While the entire exterior of conduits 20 could be catalyst coated, as a practical matter catalyst coatings should not be applied where the channels touch one another or the casing 10. This allows close fabrication and assembly tolerances, without concern for variable coating thickness, and allows for welding or brazing of metal-to-metal contact points, if desired.
  • the reactor can also incorporate streamwise variation of the fluid velocities. Specifically, the velocity of the fluid in the exothermic catalytic reaction channel can be decreased after the fluid enters the channel by streamwise geometric changes in the reactor wherein the channel's entrance flow area is less than the channel's cross-stream flow area at some streamwise location where catalyst 50 is deposited.
  • the channel's entrance flow area is defined as the channel's cross-stream flow area immediately downstream of the most downstream conduit inlet. If the conduit wall thicknesses are approximately constant, streamwise changes in flow velocity can be produced by providing, for example, either contracted sections of the conduits 20, expanded sections of the casing 10, or a combination of both.
  • the cross-stream area of conduits 20 decreases just after the cooling flow enters the cooling passages, where the expanded conduit sections taper down to the nominal conduit size in the central portion of the reactor.
  • the cooling flow velocity is increased to a value greater than its entrance velocity.
  • the casing 10 is of constant cross-sectional size, the cross-stream flow area of the exothermic catalytic reaction channel increases just after the fuel/oxidant mixture enters. As a result, the flow velocity in the exothermic catalytic reaction channel is decreased to a value less than its entrance velocity.
  • the gas flow velocity entering the exothermic catalytic reaction channel should exceed the minimum required to prevent flashback into the fuel/oxidant stream upstream of the reactor if the fuel/oxidant mixture entering the exothermic catalytic reaction channel is within the limits of flammability.
  • the laminar flame propagation velocity (velocity of a laminar deflagration wave) is typically less than 1 m/s for hydrocarbon fuels in air, but the turbulent flame propagation velocity may exceed 10 m/s and may approach 30 m/s for highly turbulent flow.
  • the gas flow velocity should exceed 10 to 30 m/s at gas turbine engine conditions, or more if a safety margin is allowed.
  • the velocity of the fuel/air stream once it has entered the exothermic catalytic reaction channel is desirable to reduce the velocity of the fuel/air stream once it has entered the exothermic catalytic reaction channel, by for example a streamwise variation of cross-stream area as discussed above.
  • the flow velocity of the fuel/air stream over the exothermic reaction surface (oxidation catalyst) in the exothermic catalytic reaction channel is nominally 30 m/s or less. This reduction in velocity is achieved by a streamwise increase in the cross-stream area for flow over the exothermic reaction surface. Streamwise changes in cross-stream area are fixed by the geometry of the reactor, and do not change in time.
  • the velocity of the cooling stream should exceed the maximum flame propagation velocity (nominally 10 to 30 m/s or more) at the exit of the cooling conduits, if the cooling fluid exiting the cooling passages is within the limits of flammability, to prevent flashback from a downstream combustion chamber.
  • the downstream increase in cross-stream area of the cooling conduits 20 is sufficiently gradual that recirculation of the cooling flow does not occur, so that there is no possibility of flashback or flameholding in the downstream expanded conduit section.
  • the cone angle for an axi-symmetric diffuser section should not exceed approximately 8 to 10 degrees for good pressure recovery and minimal recirculation. If continued backside cooling is a consideration, the angle should be especially shallow (less than 4 or 5 degrees for an axi-symmetric section) to ensure that there is no local separation of the cooling flow and concurrent loss of cooling effectiveness.
  • the cross-stream area for flow through the cooling channels is not increased after the cooling stream enters conduits 20.
  • the cross-stream area of the cooling passages may in fact be decreased to increase the cooling flow velocity for greater resistance to flashback or pre-ignition in the cooling portion of the reactor.
  • the minimum residence time for pre-ignition to occur in conduits 20 is dependent upon fuel type, fuel/air ratio, temperature, and pressure, and can be measured experimentally or calculated on the basis of elementary chemical reaction rates, if known.
  • Gas temperatures in the cooling portion of the reactor may rise to near the material limit of the catalyst and substrate (near 1200 Kelvin for precious metal catalysts), resulting in very short ignition delay times, possibly as short as 2 ms for natural gas in air at pressures near 10 atm.
  • the gas residence time in the cooling portion of the reactor should be less than the ignition delay time. Increasing the cooling flow velocity within the cooling passages reduces the residence time of the cooling fluid within the reactor, and reduces the cooling fluid's propensity for pre-ignition.
  • decreasing the velocity of the fluid in the exothermic catalytic reaction channel provides increased residence time for reaction in a given length reactor, while the cooling fluid's residence time within the same length reactor remains at a smaller value, allowing a reduced propensity for pre-ignition of the cooling fluid.
  • the reactor should be capable of providing good contact between the oxidation catalyst and the fuel/oxidant mixture in the exothermic catalytic reaction channel.
  • the reactor be sized such that the reaction of the fuel/oxidant mixture in the exothermic catalytic reaction channel should proceed more than 50% of the way to completion before exiting.
  • the percentage of reaction completed in the exothermic catalytic reaction channel depends both upon the flow rate of the fuel/oxidant mixture through the exothermic catalytic reaction channel and upon the physical characteristics of the catalytic firebox reactor.
  • the chemical composition of the fuel/oxidant mixture may also affect the percentage of reaction completed, particularly if the rate of chemical reaction is significantly limiting when compared to the rate of mass transfer to the catalyst surface.
  • important physical characteristics within the exothermic catalytic reaction channel include the rate of mass transfer to the oxidation catalyst surface, the ratio of oxidation catalyst surface area to reaction channel volume, and the activity of the oxidation catalyst.
  • the conduits are preferably between 2 mm and 8 mm in diameter, and between 75 mm and 400 mm in length, for a catalytic combustion application in which the average velocity of the fuel/air mixture entering the reactor is between 20 m/s and 100 m/s.
  • a close-packed reactor would have conduits with dimensions in approximately the same ranges as those for the square-packed reactor.
  • the fuel may comprise C1 to C20 hydrocarbons, C1 to C20 hydrocarbon oxygenates, and blends thereof.
  • Suitable gaseous fuels include natural gas, methane, and propane.
  • Suitable liquid fuels include gasoline, kerosene, No. 1 heating oil, No. 2 heating oil, and conventional aviation turbine fuels such as Jet A, Jet B, JP-4, JP-5, JP-7, and JP-8.
  • Jet A, Jet B, JP-4, JP-5, JP-7, and JP-8 "Hydrocarbon” not only refers to organic compounds, including conventional liquid and gaseous fuels, but also to gas streams containing fuel values in the form of compounds such as carbon monoxide, organic compounds, or partial oxidation products of carbon containing compounds. If the fuel is a liquid, it should be vaporized or atomized before mixing with oxidant or while being mixed with oxidant.
  • the exothermic catalytic portion of the catalytic firebox reactor may have as an active ingredient precious metals, group VIII noble metals, base metals, metal oxides, or any combination thereof.
  • Elements such as zirconium, vanadium, chromium, manganese, copper, platinum, palladium, osmium, iridium, rhodium, ruthenium, cerium, cobalt, nickel, iron, and the like may be used.
  • Platinum and palladium are preferred, palladium being especially preferred for use with natural gas or methane fuels.
  • the oxidation catalyst may be applied directly to the substrate of the reactor, or may be applied to an intermediate bond coat or washcoat composed of alumina, silica, zirconia, titania, magnesia, other refractory metal oxides, or any combination thereof.
  • the washcoat may be stabilized by the addition of additives such as lanthanum, cerium, barium, chromium, or other materials.
  • Alumina washcoats are preferred for use with natural gas or methane fuels.
  • the catalyst-coated substrate may be fabricated from any of various high temperature materials.
  • High temperature metal alloys are preferred, particularly alloys composed of iron, nickel, and/or cobalt, in combination with aluminum, chromium, and/or other alloying materials.
  • High temperature nickel alloys are especially preferred.
  • Other materials which may be used include ceramics, metal oxides, intermetallic materials, carbides, and nitrides.
  • Metallic substrates are most preferred due to their excellent thermal conductivity, allowing effective backside cooling of the catalyst.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Claims (19)

  1. Réacteur à foyer catalytique, comprenant :
    un boîtier (10) comportant une entrée et une sortie, et une surface intérieure et une surface extérieure, la surface intérieure de boîtier définissant une chambre intérieure ;
    au moins deux conduits (20), chaque conduit comportant une entrée et une sortie, et
    une surface intérieure et une surface extérieure, les conduits (20) étant retenus à l'intérieur de la chambre intérieure, les surfaces extérieures de conduits et la surface intérieure de boîtier formant un canal de réaction catalytique exothermique (60) comportant une sortie, la sortie de canal de réaction catalytique exothermique et les sorties de conduit étant positionnées à proximité de sorte qu'un premier fluide (80a) lorsqu'il sort de la sortie de conduit soit en contact avec un second fluide (80b) qui est sorti du canal de réaction catalytique exothermique (60), caractérisé par un catalyseur à oxydation (50) déposé à l'intérieur du canal de réaction catalytique exothermique (60) sur au moins une partie d'au moins une des surfaces extérieures de conduit, dans lequel le canal de réaction catalytique exothermique (60) forme un canal non divisé, dans lequel lesdits conduits (20) forment des conduits (20) pour un fluide de refroidissement passant à travers les conduits (20) pour un refroidissement côté arrière dudit catalyseur à oxydation (50), dans lequel aucun catalyseur à oxydation n'est déposé sur une surface adjacente ou opposée en contact avec un tel fluide de refroidissement.
  2. Réacteur à foyer catalytique selon la revendication 1, dans lequel les conduits (20) sont retenus par un élément de retenue (36, 37), les conduits (20) passant à travers l'élément de retenue (36, 37), et étant reliés à celui-ci et l'élément de retenue (36, 37) étant relié audit boîtier (10), l'élément de retenue (36, 37) comportant des passages (70a, 70b) à travers celui-ci.
  3. Réacteur à foyer catalytique selon la revendication 1, dans lequel les conduits (20) sont retenus à l'intérieur du boîtier (10) par une structure de fixation comprenant un premier élément de retenue (33) qui est ouvert au passage de fluide, relié audit boîtier (10) en amont des entrées de conduit, et un second élément de retenue (34) qui est ouvert au passage de fluide, relié audit boîtier (10) en aval des sorties de conduit, dans lequel au moins un parmi deux conduits adjacents quelconques (20) possède au moins une section transversale localement agrandie (15), moyennant quoi lors du rassemblement avec le conduit adjacent (20), il crée le canal de réaction catalytique exothermique (60).
  4. Réacteur à foyer catalytique selon la revendication 3, dans lequel il y a au moins deux sections transversales localement agrandies (15), une première section transversale (15) positionnée près de l'entrée de conduit et une seconde section transversale (15) positionnée près de la sortie de conduit.
  5. Réacteur à foyer catalytique selon la revendication 1, dans lequel les conduits (20) sont retenus en reliant les conduits les uns aux autres, formant une faisceau, le faisceau étant relié audit boîtier (10), dans lequel au moins un parmi deux conduits adjacents quelconques (20) possède au moins une première section transversale agrandie (15), la première section transversale agrandie (15) étant suffisante pour créer le canal de réaction catalytique exothermique.
  6. Réacteur à foyer catalytique selon la revendication 5, dans lequel le conduit (20) avec la première section transversale agrandie (15) possède une seconde section transversale agrandie (15), la première section transversale agrandie (15) étant positionnée près de l'entrée de conduit et la seconde section transversale agrandie (15) étant positionnée près de la sortie de conduit.
  7. Réacteur à foyer catalytique selon la revendication 1, dans lequel les conduits (20) sont retenus par une fixation unique, moyennant quoi les conduits (20) sont libres de s'agrandir axialement.
  8. Réacteur à foyer catalytique selon la revendication 7, dans lequel la fixation unique est un élément de retenue (36), l'élément de retenue étant ouvert au passage de fluide, l'élément de retenue (3 6) étant fixé audit boîtier.
  9. Réacteur à foyer catalytique selon la revendication 7, dans lequel au moins un parmi deux conduits adjacents quelconques (20) possède au moins une section transversale localement agrandie (15) de sorte que, lors du rassemblement avec des conduits adjacents (20), les conduits soient latéralement positionnés à l'intérieur de la chambre intérieure, et les moyens de fixation sont un faisceau créé en reliant des conduits adjacents dans un emplacement de fixation unique et en reliant le faisceau audit boîtier (10).
  10. Réacteur à foyer catalytique selon la revendication 7, dans lequel ledit emplacement de fixation unique est près de l'extrémité amont desdits conduits (20).
  11. Réacteur à foyer catalytique selon la revendication 1, comprenant :
    un premier élément de retenue (33, 36) positionné dans la chambre intérieure, relié audit boîtier (10), le premier élément de retenue (33, 36) étant ouvert au passage de fluide ;
    un second élément de retenue (34, 37) positionné à l'intérieur de ladite chambre intérieure en aval du premier élément de retenue (33, 36), relié audit boîtier (10), le second élément de retenue étant ouvert au passage de fluide ;
    dans lequel les conduits (20) sont positionnés longitudinalement à l'intérieur de la chambre intérieure, les conduits (20) étant reliés à l'éléments de retenue.
  12. Réacteur à foyer catalytique selon la revendication 1, dans lequel chaque conduit possède une première section transversale agrandie (15) et une seconde section transversale agrandie (15), les première et seconde sections transversales étant suffisantes pour créer ledit canal de réaction catalytique exothermique (60) comportant une sortie, le canal de réaction catalytique exothermique (60) étant défini par la surface intérieure dudit boîtier (10) et les surfaces extérieures de conduits, dans lequel les premières sections transversales agrandies (15) sont reliées les unes aux autres, créant un faisceau, le faisceau étant relié audit boîtier (10).
  13. Réacteur à foyer catalytique selon la revendication 12, dans lequel la première section transversale agrandie (15) est similaire et supérieure à la section transversale de conduit nominale.
  14. Réacteur à foyer catalytique selon la revendication 13, dans lequel la seconde section transversale agrandie (15) est similaire et supérieure à la section transversale de conduit nominale.
  15. Réacteur à foyer catalytique selon la revendication 1, comprenant :
    un élément de retenue d'entrée (36) comportant une face amont et une face aval,
    l'élément de retenue d'entrée (36) étant relié audit boîtier (10) à l'intérieur de l'entrée de boîtier ;
    un élément de retenue de sortie (37) comportant une face amont et une face aval,
    l'élément de retenue de sortie étant relié audit boîtier (10) à l'intérieur de la sortie de boîtier ;
    dans lequel les conduits (20) sont positionnés longitudinalement à l'intérieur de la chambre intérieure, les conduits (20) s'étendant à travers l'élément de retenue d'entrée (36) et l'élément de retenue de sortie (37), les conduits étant positionnés par l'élément de retenue d'entrée (36) et l'élément de retenue de sortie (37), les surfaces extérieures de conduit et la surface intérieure de boîtier formant ledit canal de réaction catalytique exothermique comportant une sortie.
  16. Réacteur à foyer catalytique selon la revendication 15, dans lequel les conduits (20) sont reliés à l'élément de retenue d'entrée (36).
  17. Réacteur à foyer catalytique selon la revendication 15, dans lequel les conduits (20) possèdent une premier agrandissement (15) sur le côté amont de l'élément de retenue d'entrée (36) et un second agrandissement (15) sur le côté aval de l'élément de retenue de sortie (37), lesdits premier et second agrandissements étant suffisants pour empêcher le passage du conduit (20) à travers l'élément de retenue (36, 37), moyennant quoi les conduits (20) sont retenus entre l'élément de retenue d'entrée (36) et l'élément de retenue de sortie (37) sans fixation.
  18. Procédé pour créer un mélange combustible/oxydant réactif, ledit procédé comprenant les étapes consistant à :
    faire passer un premier mélange combustible/oxydant dans le canal de réaction catalytique exothermique (60) du réacteur catalytique selon une quelconque des revendications précédentes ;
    simultanément faire passer un second mélange combustible/oxydant dans les conduits (20) dudit réacteur catalytique ; et
    associer l'effluent de conduit et l'effluent de canal de réaction.
  19. Procédé selon la revendication 18, dans lequel ledit premier mélange combustible/oxydant et ledit second mélange combustible/oxydant proviennent de la même source, et la première étape du procédé consiste à diviser un mélange combustible/oxydant en premier et second mélanges combustible/oxydant.
EP00921557A 2000-03-31 2000-03-31 Procede et appareil pour un reacteur a foyer catalytique Expired - Lifetime EP1269076B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2000/008585 WO2001075364A1 (fr) 2000-03-31 2000-03-31 Procede et appareil conçus pour un reacteur a foyer catalytique

Publications (3)

Publication Number Publication Date
EP1269076A1 EP1269076A1 (fr) 2003-01-02
EP1269076A4 EP1269076A4 (fr) 2009-11-04
EP1269076B1 true EP1269076B1 (fr) 2011-08-24

Family

ID=21741220

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00921557A Expired - Lifetime EP1269076B1 (fr) 2000-03-31 2000-03-31 Procede et appareil pour un reacteur a foyer catalytique

Country Status (5)

Country Link
EP (1) EP1269076B1 (fr)
AT (1) ATE521854T1 (fr)
AU (1) AU2000241857A1 (fr)
CA (1) CA2402322C (fr)
WO (1) WO2001075364A1 (fr)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5573330A (en) * 1978-11-27 1980-06-03 Kawasaki Heavy Ind Ltd Use of catalyst reactor
US4305910A (en) * 1979-02-28 1981-12-15 Mitsui Engineering And Shipbuilding Co., Ltd. Catalytic reaction for reduction of nitrogen oxide
JPS61259013A (ja) * 1985-05-13 1986-11-17 Babcock Hitachi Kk 触媒燃焼装置
JPH07256115A (ja) * 1994-03-22 1995-10-09 Mitsubishi Heavy Ind Ltd 燃焼触媒
JPH09210319A (ja) * 1996-02-05 1997-08-12 Mitsubishi Heavy Ind Ltd 燃焼触媒
JPH09217905A (ja) * 1996-02-09 1997-08-19 Mitsubishi Heavy Ind Ltd 燃焼触媒
US6174159B1 (en) * 1999-03-18 2001-01-16 Precision Combustion, Inc. Method and apparatus for a catalytic firebox reactor

Also Published As

Publication number Publication date
WO2001075364A1 (fr) 2001-10-11
ATE521854T1 (de) 2011-09-15
EP1269076A4 (fr) 2009-11-04
CA2402322A1 (fr) 2001-10-11
AU2000241857A1 (en) 2001-10-15
CA2402322C (fr) 2007-07-24
EP1269076A1 (fr) 2003-01-02

Similar Documents

Publication Publication Date Title
US6174159B1 (en) Method and apparatus for a catalytic firebox reactor
EP1844844B1 (fr) Réacteur catalytique
US6752623B2 (en) Method and apparatus for a fuel-rich catalytic reactor
US6887067B2 (en) Catalytically operating burner
US5342591A (en) Catalytic method
US5518697A (en) Process and catalyst structure employing intergal heat exchange with optional downstream flameholder
EP1205712B1 (fr) Régulateur d'écoulement pour une chambre de combustion catalytique pour créer une distribution homogène de la vitesse de gaz
US20020015931A1 (en) Conduit positioner
US7934925B2 (en) Catalyzer
EP1844845A2 (fr) Réacteur catalytique avec un mélangeur statique
JPH07507863A (ja) 接触燃焼
EP0745180B1 (fr) Procede et structure catalytiques ameliores assurant un echange thermique integral avec eventuellement une flamme entretenue en aval
EP1269076B1 (fr) Procede et appareil pour un reacteur a foyer catalytique
WO1999067570A2 (fr) VEILLEUSE A CATALYSEUR SEC ET A FAIBLE EMISSION DE NOx
US6155819A (en) Dry, low NOx catalytic pilot
US7521028B2 (en) Catalytic reactor for low-Btu fuels
Chen Highly exothermic process characteristics of catalytic reactors with integral heat exchange structures
WO2003025466A1 (fr) Procede de fonctionnement bicombustible d'un reacteur catalytique a melange riche de combustibles

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20021010

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

A4 Supplementary search report drawn up and despatched

Effective date: 20091001

17Q First examination report despatched

Effective date: 20100416

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 60046371

Country of ref document: DE

Effective date: 20111103

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20110824

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110824

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110824

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111226

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110824

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 521854

Country of ref document: AT

Kind code of ref document: T

Effective date: 20110824

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110824

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110824

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110824

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20120403

Year of fee payment: 13

Ref country code: CH

Payment date: 20120326

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110824

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20120323

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110824

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20120322

Year of fee payment: 13

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20120525

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 60046371

Country of ref document: DE

Effective date: 20120525

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120331

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111205

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20130331

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20131129

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60046371

Country of ref document: DE

Effective date: 20131001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130402

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131001

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130331

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120331