EP1335163A1 - Brenner für Prozessheizung mit sehr niedriger NOx Emission - Google Patents

Brenner für Prozessheizung mit sehr niedriger NOx Emission Download PDF

Info

Publication number
EP1335163A1
EP1335163A1 EP03001381A EP03001381A EP1335163A1 EP 1335163 A1 EP1335163 A1 EP 1335163A1 EP 03001381 A EP03001381 A EP 03001381A EP 03001381 A EP03001381 A EP 03001381A EP 1335163 A1 EP1335163 A1 EP 1335163A1
Authority
EP
European Patent Office
Prior art keywords
fuel
flame
ultra low
burner
staging
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.)
Granted
Application number
EP03001381A
Other languages
English (en)
French (fr)
Other versions
EP1335163B2 (de
EP1335163B1 (de
Inventor
Mahendra Ladharam Joshi
Kevin Ray Heier
Aleksandar Georgi Slavejkov
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.)
Air Products and Chemicals Inc
Original Assignee
Air Products and Chemicals 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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27615981&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1335163(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from US10/062,597 external-priority patent/US6752620B2/en
Priority claimed from US10/067,450 external-priority patent/US6773256B2/en
Application filed by Air Products and Chemicals Inc filed Critical Air Products and Chemicals Inc
Priority to DE60308071T priority Critical patent/DE60308071T3/de
Publication of EP1335163A1 publication Critical patent/EP1335163A1/de
Application granted granted Critical
Publication of EP1335163B1 publication Critical patent/EP1335163B1/de
Publication of EP1335163B2 publication Critical patent/EP1335163B2/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • F23D14/48Nozzles
    • F23D14/58Nozzles characterised by the shape or arrangement of the outlet or outlets from the nozzle, e.g. of annular configuration
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23CMETHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C5/00Disposition of burners with respect to the combustion chamber or to one another; Mounting of burners in combustion apparatus
    • F23C5/08Disposition of burners
    • F23C5/32Disposition of burners to obtain rotating flames, i.e. flames moving helically or spirally
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23CMETHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C6/00Combustion apparatus characterised by the combination of two or more combustion chambers or combustion zones, e.g. for staged combustion
    • F23C6/04Combustion apparatus characterised by the combination of two or more combustion chambers or combustion zones, e.g. for staged combustion in series connection
    • F23C6/045Combustion apparatus characterised by the combination of two or more combustion chambers or combustion zones, e.g. for staged combustion in series connection with staged combustion in a single enclosure
    • F23C6/047Combustion apparatus characterised by the combination of two or more combustion chambers or combustion zones, e.g. for staged combustion in series connection with staged combustion in a single enclosure with fuel supply in stages
    • 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
    • F23D14/20Non-premix gas burners, i.e. in which gaseous fuel is mixed with combustion air on arrival at the combustion zone
    • F23D14/22Non-premix gas burners, i.e. in which gaseous fuel is mixed with combustion air on arrival at the combustion zone with separate air and gas feed ducts, e.g. with ducts running parallel or crossing each other
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23MCASINGS, 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
    • F23M5/00Casings; Linings; Walls
    • F23M5/02Casings; Linings; Walls characterised by the shape of the bricks or blocks used
    • F23M5/025Casings; Linings; Walls characterised by the shape of the bricks or blocks used specially adapted for burner openings
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23CMETHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C2201/00Staged combustion
    • F23C2201/20Burner staging
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23CMETHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C2202/00Fluegas recirculation
    • F23C2202/40Inducing local whirls around flame
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23DBURNERS
    • F23D2900/00Special features of, or arrangements for burners using fluid fuels or solid fuels suspended in a carrier gas
    • F23D2900/00011Burner with means for propagating the flames along a wall surface

Definitions

  • the present invention is directed to a gaseous fuel burner for process heating.
  • the present invention is directed to a burner for process heating which yields ultra low nitrogen oxides (NOx) emissions.
  • NOx nitrogen oxides
  • LNBs Low NOx Burners
  • Table I Source: North American Air Pollution Control Equipment Market, Frost & Sullivan
  • An objective for new burners is to target the industrial sectors that have the largest need for LNBs based on geographic region and local air emission regulations.
  • NOx Nitrogen oxides
  • LNBs In order to comply cost-effectively for NOx emissions, many combustion equipment manufacturers have developed LNBs. See, e.g ., D. Keith Patrick, "Reduction and Control of NOx Emissions from High Temperature Industrial Processes", Industrial Heating , March 1998.
  • the cost effectiveness of an LNB compared to the SCR system would generally depend on the type of burner, consistent NOx emissions from burner, burner costs and local compliance levels.
  • the LNBs (for > 40 MM Btu/hr) have not been capable of producing low enough NOx emissions to comply with regulations or provide an alternative to SCR units. Therefore, SCR remains today as the only best available control technology for large process heaters and utility boilers.
  • the greatest challenge in designing a low NOx burner is keeping NOx emissions consistently at sub 9 ppmv level or comparable to NOx emissions at the outlet of the SCR system.
  • the prior art includes low NOx or ultra low NOx burners that produce low NOx emissions using various fuel/oxidant mixing techniques, fuel/oxidant staging techniques, flue gas recirculation, stoichiometry variations, fluid oscillations, gas reburning and various combustion process modifications.
  • most burners are unable to produce NOx emissions at less than 9 ppmv and those that do so in a lab, cannot reproduce such NOx levels in an industrial setting.
  • the technical reasons or challenges in designing a sub 9 ppmv low NOx burner will become evident as described below.
  • nozzle mixing type burners Most large capacity gaseous fuel fired industrial burners used for process heating applications are nozzle mixing type burners. As the name implies, the gaseous fuel and combustion air do not mix until they leave various fuel/oxidant ports of this type of burner.
  • the principal advantages of nozzle mix burners over premix burners are: (1) the flames cannot flash back, (2) a wider range of operating stoichiometry; and (3) a greater flexibility in burner/flame design.
  • most nozzle mix air-fuel burners require some kind of flame holder/arrester for maintaining flame stability.
  • FIG. 1 One prior art generic nozzle mix burner is shown in FIG. 1, where a metallic flame holder disk is used for providing flame stability.
  • combustion air is induced surrounding the main fuel pipe with flame holder in a large box type burner shell.
  • FIG. 1 shows staging fuel for secondary combustion to reduce overall NOx formation.
  • FIG. 2 shows a typical flame holder geometry in which a multiple-hole fuel nozzle is located in the center and several perforated slots are used on the flame holder conical disk outside for passing through a small amount of combustion air for mixing with the injected fuel.
  • the bluff body shape flame holder creates an air stream reversal as shown in FIG. 2.
  • the opposite direction air stream creates almost stagnant condition (zero axial velocity) for air fuel mixing at the inside cavity of the flame holder cone. This stagnant air-fuel mixture with almost no positive firing axis velocity component is used for attaching the main flame to the flame holder base.
  • Flame holders of various hole patterns and external shapes are used for anchoring flames.
  • U. S. Patent No. 5,073,105 (Martin, et al.) and U.S. Patent No. 5,275,552 (Schwartz et al.) describe low NOx burner devices where such flame holders are used to anchor the flame.
  • a primary fuel (30 - 50% of total fuel) is injected radially inwardly over the flame holder disk with flue gas entrainment (through a hole in the burner tile) for anchoring the primary flame.
  • the remaining, secondary fuel is injected surrounding and impacting the external burner block (tile) surface for fuel staging and furnace gas recirculation. Combustion air mixing with the primary fuel takes place inside the burner block over the flame holder and some NOx is formed due to limited heat dissipation volume inside the burner block cavity and due to creation of locally fuel rich regions.
  • a main disadvantage associated with flame holders for use in ultra low-NOx burners is localized stagnant zones of fuel-rich combustion that are generally anchored at the inner base of a flame holder cone or disk. These zones are located on the solid ridges between adjacent air slots/holes due to pressure conditions created by the outer air stream.
  • burners with limited flame stability may experience blow-off of flame, thereby creating a hazard and delaying production.
  • a remedy could be to use a second set of burners specially designed for heat-up conditions, which can be costly as well as manpower intensive.
  • the present invention is directed to an ultra low NOx gaseous fuel burner for process heating applications such as utility boilers, process heaters and industrial furnaces.
  • the novel burner utilizes two unique inter-dependent staged processes for generating a non-luminous, uniform and combustion space filling flame with extremely low ( ⁇ 9 ppmv) NOx emissions. This is accomplished using: (1) a flame stabilizer such as a large scale vortex device upstream to generate a low firing rate, well-mixed, low-temperature and highly fuel-lean (phi 0.05 to 0.3) flame for maintaining the overall flame stability, and (2) multiple uniformly spaced and diverging fuel lances downstream to inject balanced fuel in several turbulent jets inside the furnace space for creating massive internal flue gas recirculation.
  • the resulting flame provides several beneficial characteristics such as no visible radiation, uniform heat transfer, lower flame temperatures, combustion space filling heat release and production of ultra low NOx emissions.
  • the burner generates NOx emissions of less than 9 ppmv at near stoichiometry conditions.
  • the at least one hole and the divergence angles are adapted to provide complete circumferential coverage of the fuel-lean flame. In another embodiment, the at least one hole and the divergence angles are adapted to provide a flat flame pattern. In a third embodiment, the at least one hole and the divergence angles are adapted to provide a load shaping flame pattern
  • each staging nozzle has between 1 hole and 4 holes.
  • the radial divergence angle is between 8° and 24° and the axial divergence angle is between 4° and 16°.
  • the velocity of fuel exiting the nozzle is preferably between 300 to 900 feet per second for a natural gas staging fuel.
  • the distance from the forward end of the burner to a point where mixing of staging flame and flame stabilizer flame occurs is preferably approximately 8 to 48 inches.
  • the fuel rate of the staging for natural gas fuel is from 70% to 95% of the total fuel firing rate of the burner.
  • the flame stabilizer is preferably a large scale vortex device where the flame has a peak flame temperature of less than approximately 2000° Fahrenheit.
  • the burner may include a burner block coaxial to the flame stabilizer.
  • the burner block is cylindrical or slightly conical, or rectangular in shape.
  • FIG. 1 is a simplified side elevational view of a prior art air-fuel burner with a flame holder.
  • FIG. 2 is a simplified side elevational view of a prior art flame holder for an air-fuel burner.
  • FIG. 3 is a simplified side elevational view of a fluid based large scale vortex flame stabilizer for use with an ultra low NOx burner of the present invention.
  • FIG. 4A is a graphical representation of NOx emissions vs. average flame temperature.
  • FIG. 4B is a graphical representation of NOx emissions vs. excess oxygen in exhaust gas.
  • FIG. 5A is a simplified, side elevational view of an ultra low-NOx burner in a circular staging configuration in accordance with the present invention.
  • FIG. 5B is a simplified, front firing, end view of an ultra low-NOx burner in a flat staging configuration in accordance with the present invention.
  • FIG. 5C is a simplified, front firing, end view of an ultra low-NOx burner in another flat staging configuration in accordance with the present invention.
  • FIG. 6 is a simplified front and side view of fuel nozzles and flame pattern of the flame stabilizer of FIG. 3 in combination with the ultra low-NOx burner of FIG. 5A.
  • FIG. 7A is a cross-sectional, top plan view of a fuel staging nozzle used in the burner of FIG. 5A.
  • FIG. 7B is a cross-sectional, side elevational view of the fuel staging nozzle of FIG. 7A.
  • FIG. 7C is a right side view of the fuel staging nozzle of FIG 7B.
  • FIG. 8 is a simplified side elevational view of the burner of FIG. 5A depicting interaction of a flame stabilizer fuel flame and a staging fuel flame.
  • FIG. 9 is a is a graphical representation of NOx emissions with respect to oxidant/oxygen under diluted conditions.
  • FIG. 10 is a graphical representation of lab measurements of a burner flame using a suction pyrometer depicting flame temperature vs. radial distance.
  • FIG. 11A through FIG. 11D are a schematic illustrations of various flat staging configurations of ultra low-NOx burners in accordance with the present invention tested in a lab furnace.
  • FIG. 12A is a simplified illustration of a load shaping staging configuration in an industrial boiler using multiple flame stabilizers.
  • FIG. 12B is a simplified illustration of a load shaping staging configuration in an industrial boiler using a single flame stabilizer.
  • FIG. 13A is a simplified illustration of a wall-fired power boiler firing configuration with rows of stabilizers and fuel staging lances.
  • FIG. 13B is a simplified illustration of a tangential-fired power boiler firing configuration with rows of stabilizers and fuel staging lances.
  • FIG. 3 a device for stabilization of a flame in the form of a large scale vortex (LSV) device 12 for use with an ultra low NOx burner 10 (see FIGS. 5A and 8) in accordance with the present invention.
  • the LSV device 12 is comprised of an inner (secondary) air or oxidant pipe 14 recessed inside a fuel pipe 16, which is further recessed inside an outer (primary) air or oxidant pipe 18.
  • the primary oxidant e.g ., air
  • the secondary oxidant e.g ., air
  • Table I gives an example of specific velocity ranges and dimensionless ratios for obtaining a stable stream-wise vortex in the primary oxidant pipe 18.
  • V pa the velocity of the primary oxidant
  • V f the velocity of the fuel
  • V sa the velocity of the secondary oxidant
  • D f the diameter of the fuel pipe 16
  • L f the distance between the forward end of the fuel pipe 16 and the forward end of the primary oxidant pipe 18
  • D pa the diameter of the primary oxidant pipe18
  • L sa the distance between the forward end of the secondary oxidant pipe 14 and the forward end of the fuel pipe 16
  • D sa the diameter of the secondary oxidant pipe 14.
  • the preferred average velocity ranges for fuel is about 2 to 6 ft/sec
  • for primary oxidant is 30 to 90 ft/sec
  • for secondary oxidant is 15 to 45 ft/sec.
  • the LSV flame stability is maintained at high excess airflow due to fluid flow reversal caused by a stream-wise vortex which, in turn, causes internal flue gas recirculation and provides preheating of air/fuel mixture and intense mixing of fuel, air and products of combustion to create ideal conditions for flame stability.
  • the LSV flame is found to anchor on the fuel pipe tip 22, i.e ., its forward end. Under normal operation, most LSV internal components remain at less than 1000°F.
  • FIGS. 4A and 4B show general NOx trends as a function of flame temperature and excess oxygen measured in the exhaust gas.
  • the LSV device 12 operation at extremely fuel lean conditions for ultra low-NOx emissions necessitates that combustion of the remaining fuel downstream be accomplished in a strategic manner to complete combustion, to avoid additional NO or CO formation, and to operate the burner system with a slight overall excess of oxygen (2 to 3%) in the exhaust.
  • FIG. 5A shows a schematic of the ultra low-NOx burner 10 in accordance with the present invention which combines the aforementioned LSV device 12 with strategic fuel staging lances 24 in a circular configuration.
  • the overall burner process can be described in three process elements: 1) extremely fuel-lean combustion, 2) large scale vortex for flame stability, and 3) fuel staging using strategically located fuel lances 24.
  • the LSV device 12 is surrounded in a cage type construction using multiple fuel staging lances 24.
  • the lances 24 are long steel pipes with specially designed staging nozzles 26 at the firing end. According to lab experiments, the optimum number of staging lances 24 can vary from 4 to 16 and each staging lance 24 has multiple diverging holes 28 (see FIGS.
  • the number of holes 28 per staging nozzle 26 can vary from a single hole for a less than 1 MM Btu/hr burner to, for example, 4 holes for higher firing rate burners.
  • the number of staging holes 28 and their divergence angles (alpha and beta as described below) are chosen to accomplish complete circumferential coverage of the LSV flame for a circular configuration (see FIG. 5A), a flat configuration (see FIGS. 5B and 5C) or to accomplish a load shaping pattern (see FIGS. 12A and 12B).
  • FIG. 6 shows a schematic for a 4 MM Btu/hr burner with a 10 inch diameter burner block.
  • Eight uniformly distributed staging fuel lances 24 (on a 7 inch pitch circle radius) and two diverging holes per staging lance provide a circular pattern.
  • FIGS. 7A, 7B and 7C show one typical design of staging lance nozzle 26 and geometry of staging holes 28 (note angles alpha and beta).
  • the complete envelope of staging fuel that is significantly diluted with combustion gases produces a very low temperature and combustion space filling flame.
  • the preferred range for angle alpha is between 8° and 24° and for angle beta is between 4° and 16°.
  • the holes 28 vary in size depending on staging fuel injection velocity range.
  • the preferred nozzle exit velocity range is between 300 to 900 feet per second for natural gas staging fuel.
  • For a single hole staging nozzle preferably, only an axial divergence angle alpha is used.
  • the above velocities (or nozzle hole sizes) vary depending on the fuel composition (and heating value) and burner firing capacity.
  • the complete ultra low NOx burner with LSV flame upstream and fuel staging downstream is illustrated in FIG. 8.
  • the various combustion processes are also shown. Referring to FIG. 8, the various burner flame processes are now described:
  • the LSV flame has a very low peak flame temperature (less than ⁇ 2000° Fahrenheit) and produces very low NOx emissions. This is due to excellent mixing, avoidance of fuel-rich zones for prompt NOx formation (as observed in traditional flame holders) and completion of overall combustion under extremely fuel-lean conditions.
  • the recycling of exhaust gas in the LSV device 12 also reduces flame temperature due to product gas dilution. Table II gives laboratory firing data on the LSV device 12 under fuel lean firing conditions.
  • LSV device 12 produces very low NOx emissions at low firing rates and under extremely fuel-lean conditions.
  • high oxygen concentration and low CO 2 concentration indicate excess air operation accompanied by leakage of outside are through refractory cracks in the lab furnace.
  • the LSV device 12 is generally fired at equivalence rations of 0.05 to 0.1. For example, if there is a total firing rate of 4 MM Btu/hr, the LSV device 12 is firing at 0.4 MM Btu/hr, and fuel staging lances 24 are set to inject fuel at 3.6 MM Btu/hr, the LSV device 12 will then supply total combustion air for 4 MM Btu/hr or air at a 900% level for 0.4 MM Btu/hr firing rate.
  • the LSV flame is extremely fuel-lean, it is diluted with combustion air, and products of combustion from vortex action and the resulting peak flame temperature (as measured by a thermocouple probe before staging fuel jets meet the LSV flame) are less than 2000° Fahrenheit.
  • the merge distance, X, between the LSV flame and the staging jets from the furnace wall is maintained at approximately 8 to 48 inches from the end of the burner and this distance depends on the burner-firing rate and staging fuel divergence angle (beta). For a 4 MM Btu/hr total firing rate, a measured merge distance was approximately 24". This distance is critical in keeping the flame free from visible radiation, providing combustion space filling characteristics, having low peak flame temperatures, and producing ultra low NOx emissions.
  • the dilution of combustion air using LSV products of combustion is also very important for reducing localized oxygen availability. For example, if 36,000 scfh of combustion air (at ambient temperature) is mixed with approximately 1500°F products of combustion from an LSV device 12 firing at 0.40 MM Btu/hr firing rate, there is a localized dilution of combustion air. Additionally, oxygen concentration in the combustion air decreases from about 21% to 19%. This reduction in oxygen availability (which may be higher locally due to volumetric gas expansion) can reduce NOx emissions further when already diluted staging fuel reacts with the preheated air of reduced oxygen concentration. This dual effect of fuel dilution and air dilution are explained'below under Circular Staging configuration.
  • Peak temperatures of the spacious flame occur outside the center core region of overall flame.
  • the temperature profile is a reflection of circular staging pattern and lower temperatures exist in the core region due to fuel-lean LSV products of combustion.
  • the peak flame temperatures never exceeded 2100° Fahrenheit at any transverse cross section along furnace length.
  • the fuel staging is performed using a circular staging configuration with multiple diverging lances 24 installed around the LSV device 12 or the burner block 17 exterior.
  • the fuel jets are injected in the furnace space using nozzles 26 of specific hole geometry. See FIGS. 7A, 7B, and 7C.
  • the resulting combustion (above auto ignition temperature) is controlled by chemical kinetics and by fuel jet mixing with the furnace gases and oxidant.
  • the carbon contained in the fuel molecule is drawn to complete oxidation with the diluted oxidant stream instead of the pyrolitic soot forming reactions of a traditional flame front.
  • combustion takes place in two stages: In the first stage, fuel is converted to CO and H 2 in diluted, fuel rich conditions. Here, the dilution suppresses the peak flame temperatures and formation of soot species, which would otherwise produce a luminous flame.
  • CO and H 2 react with diluted oxidant downstream to complete combustion and form CO 2 and H 2 O. This space-based dilution and staged combustion leads to a space filling process where a much larger space surrounding flame is utilized to complete the overall combustion process.
  • a fuel jet significantly diluted (with N 2 , CO 2 and H 2 O) using furnace gas entrainment can readily react with furnace-oxidant to form a combustion space filling low-temperature flame.
  • the Handbook of Combustion, Vol. II illustrates lower NOx formation under diluted conditions as shown in FIG. 9.
  • FIG. 9 it is shown that the oxygen available under diluted conditions for NOx formation is further curtailed if oxidant is preheated to higher preheat temperatures.
  • the LSV device 12 supplies a preheated oxidant stream, which is also diluted in oxygen concentration due to mixing with it own products of combustion.
  • the amount of fuel staging (for natural gas fuel) can be anywhere from 70% to 95% of the total firing rate of the burner. This range provides extremely low NOx emissions (1 to 9 ppmv). Fuel staging range less than 70% can be used for spacious combustion if NOx emissions are not of concern. The fuel staging range above 95% can be used for gases containing hydrogen, CO or other highly flammable gases.
  • the data in Table IV indicate that overall NOx emissions are less than 5 ppmv (corrected at 3% excess oxygen) for 1 to 6 MM Btu/hr firing capacity.
  • the flame was completely non-luminous and combustion space filling between 2 to 6 MM Btu/hr firing capacity.
  • the fuel staging hole diameter for above tests was 0.11 inches. This provided an average natural gas injection velocity of 300 to 900 feet per second in the firing range of 2 to 6 MM Btu/hr.
  • the burner also used less than 1.5 inches of water column pressure drop for the combustion air in the LSV device.
  • the preferred construction of the ultra low NOx burner uses concentric standard steel pipes or standard tubes welded in a telescopic fashion to satisfy the key LSV flow, velocity and dimensionless ratios (see above).
  • a 4 MM Btu/hr. nominal firing rate LSV device 12 may be built using standard 3 inch Schedule 40 pipe for the secondary oxidant pipe 14, a 6 inch Schedule 40 pipe for the fuel pipe 16, and an 8 inch Schedule 40 pipe for the primary oxidant pipe.
  • the burner block 17 (see FIG. 8) may be built using standard 10 inch Schedule 40 pipe.
  • the lances 24 may be 1 ⁇ 2 inch schedule 40 pipe with nozzles 26 welded or threaded thereon.
  • These pipes may be made from, for example, carbon steel, aluminized steel, stainless steel, or high temperature alloy steels.
  • the cylindrical burner block 17 for the LSV flame is sized using a standard pipe size.
  • the burner block 17 may be sized one or two pipe sizes larger than the primary oxidant pipe 18 in the LSV device 12.
  • the primary oxidant pipe 18 may be an 8 inch Schedule 10 pipe.
  • the burner block was selected as 10 inch 40 pipe (one standard pipe size larger).
  • the burner block 17 length is generally the same as the furnace wall thickness ( e.g ., about 12" to 14").
  • the design objective of the cylindrical burner block is to avoid LSV flame interference on the inside surface of the burner block, keeping burner block material cool (preventing thermal damage), and reducing the frictional pressure drop for the incoming combustion air.
  • the burner block cavity is preferred to be cylindrical or slightly conical (half cone angle less than 10°) in shape for several reasons.
  • the staging fuel may enter the low-pressure recirculation region inside burner block cavity to initiate premature combustion and overheating.
  • FIGS. 5B and 5C Schematic diagrams of flat staging configurations are shown in FIGS. 5B and 5C.
  • the staging lances 24a, 24b are placed in a linear fashion on both left and right sides of an LSV device 12a, 12b.
  • burner blocks 17a FIG. 5B
  • 17b FIG. 5C
  • the flame envelopes 30a, 30b are shown in dotted lines.
  • the separation distances "s" (see FIG. 5B) and “h” (see FIG. 5C) were determined experimentally based on NOx reduction and least amount of CO formation. The optimum distance based on burner firing range lie between 2 and 12 inches.
  • FIGS. 5B and 5C Schematic diagrams of flat staging configurations are shown in FIGS. 5B and 5C.
  • the staging lances 24a, 24b are placed in a linear fashion on both left and right sides of an LSV device 12a, 12b.
  • burner blocks 17a FIG. 5B
  • 17b FIG. 5C
  • FIGS. 11 A through 11D show several flat staging configurations for 4 MM Btu/Hr total firing rate and approximately 1500°F average furnace operating temperature.
  • the lances 24, 24d, 24e, 24f were of various holes sizes, number of holes, and various radial and axial divergence angles. These values are noted in FIGS. 11 A through 11 D.
  • the lance locations and hole geometry was varied to understand the effect on staging fuel supply pressure as well as emissions of NO and CO. It was noticed that higher staging fuel supply pressure produced lower NOx emissions and Vice-versa.
  • Some hydrogen furnaces in particular, reformers, which are direct-fired chemical reactors consisting of numerous tubes located in the furnace (firebox) and filled with catalyst. Conversion of hydrocarbon and steam to an equilibrium mixture of hydrogen, carbon oxides and residual methane takes place inside the catalyst tubes. Heat for the highly endothermic reaction is provided by burners in the firebox.
  • a Large Steam Methane Reformer (SMR) is usually of a top fired design. Top fired reformers have multiple rows of tubes in the firebox. The burners, for example, as many as 150, are located in an arch on each side of the tubes and heat is transferred to the tubes by radiation from the products of combustion. A burner utilizing flat staging would be ideal for top-fired SMR furnaces.
  • the ultra low NOx burner is configured in the shape identical to load geometry.
  • Each lance 24g has a pipe having a fuel staging nozzle at a firing end thereof and having at least one hole at end for staging fuel injection, as described above for the previous embodiments.
  • Each hole has a radial divergence angle and an axial divergence angle, as described above for the previous embodiments.
  • the hole or holes and the divergence angles provide a load shape coverage.
  • the burner in this configuration also provides NOx emissions of less than 9 ppmv.
  • single or multiple LSV devices 12g, 12g' are used and fuel staging lances 24g, 24g' are strategically placed parallel to load, such as boiler water tube envelope surface 42a, 42b, geometry (square, rectangle, trapezoidal, circular, elliptical or any other load shape by combination of various primary shapes).
  • load such as boiler water tube envelope surface 42a, 42b, geometry (square, rectangle, trapezoidal, circular, elliptical or any other load shape by combination of various primary shapes).
  • the objective of above staging strategy is to entrain relatively cooler furnace gases in the vicinity of load surface (e.g. water or process tubes) and create a low-temperature overall spacious flame.
  • staging lances 24g, 24g' are used per LSV device 12g and each staging nozzle has between 1 hole and 4 holes.
  • the lances 24g, 24g' can be configured parallel to the load geometry and can be positioned in several parallel rows.
  • the radial divergence angle is between 8° and 24° and the axial divergence angle is between 0° and 16°.
  • the velocity of fuel exiting the nozzle is preferably between 300 to 900 feet per second for a natural gas staging fuel.
  • the load shaping staging can be implemented using either wall fired firing boiler 34 configuration, see FIG. 13A or tangentially fired firing configuration 36. see FIG. 13B.
  • Most power boilers are much larger in capacity and use anywhere from 10 to 20 burners per firing wall and typical firing capacity is about 1 billion Btu/hr.
  • the burners are placed in several rows and they share common manifold 38 for combustion air.
  • the low NOx burners 12g can be placed in similar geometrical locations and share common combustion air supply through a rectangular air manifold 38.
  • the most important design aspect for achieving low NOx emissions would be to use multiple fuel lances 24g on the firing wall in several rows between LSV devices 12g to create spacious flame 32.
  • Furnaces gases are entrained in the staged fuel jets before combusting with combustion air discharged from LSV device 12g.
  • the power boilers have refractory line combustion chamber or radiation zone where most of the fuel is combusted and then hot products of combustion travel upward to heat water-tubes or load in the convection zone, and then economizer section before discharged out to the stack.
  • over-fired air portion of combustion air 5 to 25%
  • Figure 13B shows tangentially-fired power boiler, where all four corners are used to create a swirling or tangential flow pattern 40 inside a square furnace radiation zone 42.
  • the combustion air supplied by air registers and the proposed low NOx burners are mounted in several rows on all four corners.
  • the load shaping fuel lances 12g can be installed in several rows between LSV devices 12g to create a tangential or swirling spacious flame.
  • each staging nozzle has between 1 hole and 4 holes.
  • the lances can be configured parallel to the load geometry and can be positioned in several parallel rows.
  • the radial divergence angle is between 8° and 24° and the axial divergence angle is between 0° and 16°.
  • the velocity of fuel exiting the nozzle is preferably between 300 to 900 feet per second for a natural gas staging fuel.
  • an oxidant with an oxygen concentration between 10 and 21% may be used or an enriched oxidant, i.e., greater than 21% and less than 50% oxygen content may be used.
  • the oxidant is at ambient conditions to a preheated level, for example, 200 degrees F to 2400 degrees F.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
EP03001381A 2002-01-31 2003-01-27 Brenner für Prozessheizung mit sehr niedrigem NOx Ausstoss Expired - Lifetime EP1335163B2 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE60308071T DE60308071T3 (de) 2002-01-31 2003-01-27 Brenner für Prozessheizung mit sehr niedrigem NOx Ausstoss

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US62597 2002-01-31
US10/062,597 US6752620B2 (en) 2002-01-31 2002-01-31 Large scale vortex devices for improved burner operation
US10/067,450 US6773256B2 (en) 2002-02-05 2002-02-05 Ultra low NOx burner for process heating
US67450 2002-02-05

Publications (3)

Publication Number Publication Date
EP1335163A1 true EP1335163A1 (de) 2003-08-13
EP1335163B1 EP1335163B1 (de) 2006-09-06
EP1335163B2 EP1335163B2 (de) 2012-05-09

Family

ID=27615981

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03001381A Expired - Lifetime EP1335163B2 (de) 2002-01-31 2003-01-27 Brenner für Prozessheizung mit sehr niedrigem NOx Ausstoss

Country Status (4)

Country Link
EP (1) EP1335163B2 (de)
AT (1) ATE338916T1 (de)
DE (1) DE60308071T3 (de)
ES (1) ES2271391T5 (de)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1605203A2 (de) * 2004-06-07 2005-12-14 Air Products And Chemicals, Inc. Brenner und Verfahren zur Verbrennung eines zur Bildung fester Produkte fähigen Gases
WO2011080780A1 (en) 2009-12-30 2011-07-07 Hysytech S.R.L. Burner and combustion device comprising said burner
EP2405197A1 (de) * 2010-07-05 2012-01-11 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Wartungsarmes Verbrennungsverfahren geeignet zur Verwendung in einem Vorherd eines Glasofens
CN101493230B (zh) * 2008-01-22 2012-10-03 通用电气公司 经由喷嘴当量比控制的燃烧贫油熄火保护
CN103380328A (zh) * 2011-01-21 2013-10-30 法国德西尼布公司 一种燃烧器和包含这种燃烧器的燃烧炉
WO2013082432A3 (en) * 2011-12-01 2014-01-16 Air Products And Chemicals, Inc. Rapid energy release burners and methods for using the same
CN103807850A (zh) * 2014-03-13 2014-05-21 杜建吉 一种用于燃气轮机余热锅炉的补燃燃烧器
EP3078910A1 (de) 2015-04-08 2016-10-12 Vysoké Ucení Technické V Brne Gasbrenner mit gestufter verbrennung
CZ306247B6 (cs) * 2015-03-09 2016-10-26 Vysoké Učení Technické V Brně Plynový hořák
JP2018146168A (ja) * 2017-03-06 2018-09-20 中外炉工業株式会社 バーナー装置及び加熱処理設備
JP2019086189A (ja) * 2017-11-02 2019-06-06 株式会社Ihi 燃焼装置及びボイラ
CN111156512A (zh) * 2020-02-13 2020-05-15 上海凌云瑞升燃烧设备有限公司 一种多品位空气助燃超低氮燃烧器
CN111810950A (zh) * 2017-09-05 2020-10-23 丰田自动车株式会社 用于氢气燃烧器装置的喷嘴结构

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9388983B2 (en) 2013-10-03 2016-07-12 Plum Combustion, Inc. Low NOx burner with low pressure drop
DE102016125526B3 (de) * 2016-12-22 2018-05-30 Max Weishaupt Gmbh Mischvorrichtung und Brennerkopf für einen Brenner mit reduziertem NOx-Ausstoß

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4505666A (en) * 1981-09-28 1985-03-19 John Zink Company Staged fuel and air for low NOx burner
US5073105A (en) 1991-05-01 1991-12-17 Callidus Technologies Inc. Low NOx burner assemblies
US5135387A (en) * 1989-10-19 1992-08-04 It-Mcgill Environmental Systems, Inc. Nitrogen oxide control using internally recirculated flue gas
US5195884A (en) 1992-03-27 1993-03-23 John Zink Company, A Division Of Koch Engineering Company, Inc. Low NOx formation burner apparatus and methods
EP0573300A2 (de) * 1992-06-05 1993-12-08 Nippon Furnace Kogyo Kaisha Ltd. Verbrennungsverfahren mit niedrigem NOx-Gehalt und Brennervorrichtung zur Durchführung des Verfahrens
US5275552A (en) 1992-03-27 1994-01-04 John Zink Company, A Division Of Koch Engineering Co. Inc. Low NOx gas burner apparatus and methods
US5284438A (en) * 1992-01-07 1994-02-08 Koch Engineering Company, Inc. Multiple purpose burner process and apparatus
US5413477A (en) 1992-10-16 1995-05-09 Gas Research Institute Staged air, low NOX burner with internal recuperative flue gas recirculation
US5667376A (en) 1993-04-12 1997-09-16 North American Manufacturing Company Ultra low NOX burner
US5957682A (en) 1996-09-04 1999-09-28 Gordon-Piatt Energy Group, Inc. Low NOx burner assembly
US6027330A (en) 1996-12-06 2000-02-22 Coen Company, Inc. Low NOx fuel gas burner

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5085577A (en) 1990-12-20 1992-02-04 Meku Metallverarbeitunge Gmbh Burner with toroidal-cyclone flow for boiler with liquid and gas fuel
US5839853A (en) 1991-10-02 1998-11-24 Oppenheimer; M. Leonard Buoyant matter diverting system
US5478167A (en) 1991-10-02 1995-12-26 Oppenheimer; M. Leonard Buoyant matter diverting system
FR2729743B1 (fr) 1995-01-24 1997-04-04 Cuenod Thermotech Sa Tete de combustion, en particulier pour bruleur a air souffle, et bruleur equipe d'une telle tete

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4505666A (en) * 1981-09-28 1985-03-19 John Zink Company Staged fuel and air for low NOx burner
US5135387A (en) * 1989-10-19 1992-08-04 It-Mcgill Environmental Systems, Inc. Nitrogen oxide control using internally recirculated flue gas
US5073105A (en) 1991-05-01 1991-12-17 Callidus Technologies Inc. Low NOx burner assemblies
US5284438A (en) * 1992-01-07 1994-02-08 Koch Engineering Company, Inc. Multiple purpose burner process and apparatus
US5195884A (en) 1992-03-27 1993-03-23 John Zink Company, A Division Of Koch Engineering Company, Inc. Low NOx formation burner apparatus and methods
US5275552A (en) 1992-03-27 1994-01-04 John Zink Company, A Division Of Koch Engineering Co. Inc. Low NOx gas burner apparatus and methods
EP0573300A2 (de) * 1992-06-05 1993-12-08 Nippon Furnace Kogyo Kaisha Ltd. Verbrennungsverfahren mit niedrigem NOx-Gehalt und Brennervorrichtung zur Durchführung des Verfahrens
US5413477A (en) 1992-10-16 1995-05-09 Gas Research Institute Staged air, low NOX burner with internal recuperative flue gas recirculation
US5667376A (en) 1993-04-12 1997-09-16 North American Manufacturing Company Ultra low NOX burner
US5957682A (en) 1996-09-04 1999-09-28 Gordon-Piatt Energy Group, Inc. Low NOx burner assembly
US6027330A (en) 1996-12-06 2000-02-22 Coen Company, Inc. Low NOx fuel gas burner

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
D.KEITH PATRICK: "Reduction and Control of NOx Emissions from High Temperature Industrial Processes.", INDUSTRIAL HEATING, 1 March 1998 (1998-03-01)
R.K.AGRAWAL AND S:C:WOOD: "Cost-Effective NOx Reduction", CHEMICAL ENGINEERING, 1 February 2001 (2001-02-01)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1605203A3 (de) * 2004-06-07 2008-04-16 Air Products And Chemicals, Inc. Brenner und Verfahren zur Verbrennung eines zur Bildung fester Produkte fähigen Gases
EP1605203A2 (de) * 2004-06-07 2005-12-14 Air Products And Chemicals, Inc. Brenner und Verfahren zur Verbrennung eines zur Bildung fester Produkte fähigen Gases
CN101493230B (zh) * 2008-01-22 2012-10-03 通用电气公司 经由喷嘴当量比控制的燃烧贫油熄火保护
WO2011080780A1 (en) 2009-12-30 2011-07-07 Hysytech S.R.L. Burner and combustion device comprising said burner
EP2405197A1 (de) * 2010-07-05 2012-01-11 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Wartungsarmes Verbrennungsverfahren geeignet zur Verwendung in einem Vorherd eines Glasofens
CN103380328B (zh) * 2011-01-21 2016-04-06 法国德西尼布公司 一种燃烧器和包含这种燃烧器的燃烧炉
CN103380328A (zh) * 2011-01-21 2013-10-30 法国德西尼布公司 一种燃烧器和包含这种燃烧器的燃烧炉
US9664381B2 (en) 2011-12-01 2017-05-30 Air Products And Chemicals, Inc. Staged oxy-fuel burners and methods for using the same
CN104067049B (zh) * 2011-12-01 2017-04-05 气体产品与化学公司 分级式氧‑燃料喷燃器及其使用方法
US9134025B2 (en) 2011-12-01 2015-09-15 Air Products And Chemicals, Inc. Rapid energy release burners and methods for using the same
WO2013082432A3 (en) * 2011-12-01 2014-01-16 Air Products And Chemicals, Inc. Rapid energy release burners and methods for using the same
CN104067049A (zh) * 2011-12-01 2014-09-24 气体产品与化学公司 分级式氧-燃料喷燃器及其使用方法
CN103807850A (zh) * 2014-03-13 2014-05-21 杜建吉 一种用于燃气轮机余热锅炉的补燃燃烧器
CN103807850B (zh) * 2014-03-13 2015-12-16 杜建吉 一种用于燃气轮机余热锅炉的补燃燃烧器
CZ306247B6 (cs) * 2015-03-09 2016-10-26 Vysoké Učení Technické V Brně Plynový hořák
EP3078910A1 (de) 2015-04-08 2016-10-12 Vysoké Ucení Technické V Brne Gasbrenner mit gestufter verbrennung
JP2018146168A (ja) * 2017-03-06 2018-09-20 中外炉工業株式会社 バーナー装置及び加熱処理設備
CN111810950A (zh) * 2017-09-05 2020-10-23 丰田自动车株式会社 用于氢气燃烧器装置的喷嘴结构
JP2019086189A (ja) * 2017-11-02 2019-06-06 株式会社Ihi 燃焼装置及びボイラ
JP7027817B2 (ja) 2017-11-02 2022-03-02 株式会社Ihi 燃焼装置及びボイラ
CN111156512A (zh) * 2020-02-13 2020-05-15 上海凌云瑞升燃烧设备有限公司 一种多品位空气助燃超低氮燃烧器

Also Published As

Publication number Publication date
EP1335163B2 (de) 2012-05-09
EP1335163B1 (de) 2006-09-06
DE60308071T3 (de) 2012-10-25
ES2271391T3 (es) 2007-04-16
DE60308071D1 (de) 2006-10-19
ES2271391T5 (es) 2012-07-02
DE60308071T2 (de) 2007-03-01
ATE338916T1 (de) 2006-09-15

Similar Documents

Publication Publication Date Title
US6773256B2 (en) Ultra low NOx burner for process heating
US11747013B2 (en) Low NOx and CO combustion burner method and apparatus
JP4309380B2 (ja) 点火支援燃料ランスを有する多段燃焼システム
KR100837713B1 (ko) 초저 NOx 버너 조립체
EP1335163B1 (de) Brenner für Prozessheizung mit sehr niedrigem NOx Ausstoss
CA2038796C (en) Apparatus and method of lowering nox emissions using diffusion processes
CA2385028C (en) Venturi cluster, and burners and methods employing such cluster
US6000930A (en) Combustion process and burner apparatus for controlling NOx emissions
EP0376259B1 (de) Kessel mit vermindertem NOx-Ausstoss
EP1729062A2 (de) Dynamische Brennerrekonfiguration und Verbrennungsvorrichtung für Heizkessel und Prozesserhitzer
US20120037146A1 (en) Low nox burner
CA2531326C (en) Oxy-fuel fired process heaters
Carroll et al. Low NO x and CO combustion burner method and apparatus
EP1559956A2 (de) Venturi-Düsengruppe und diesen nutzende Brenner und Verfahren
JPH0849812A (ja) 燃焼炉とその低NOx燃焼方法
Cao et al. Ultra-low NO x burner assembly

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

AK Designated contracting states

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO

17P Request for examination filed

Effective date: 20030901

AKX Designation fees paid

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT SE SI SK TR

17Q First examination report despatched

Effective date: 20050208

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 BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT SE SI SK TR

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;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20060906

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: 20060906

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: 20060906

Ref country code: SI

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: 20060906

Ref country code: SK

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: 20060906

Ref country code: LI

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: 20060906

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: 20060906

Ref country code: CZ

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: 20060906

Ref country code: CH

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: 20060906

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

REF Corresponds to:

Ref document number: 60308071

Country of ref document: DE

Date of ref document: 20061019

Kind code of ref document: P

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

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: 20061206

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: 20061206

Ref country code: BG

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: 20061206

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: 20070131

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

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: 20070219

ET Fr: translation filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2271391

Country of ref document: ES

Kind code of ref document: T3

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: L'AIR LIQUIDE S.A. A DIRECTOIRE ET CONSEIL DE S

Effective date: 20070606

NLR1 Nl: opposition has been filed with the epo

Opponent name: L'AIR LIQUIDE S.A. A DIRECTOIRE ET CONSEIL DE SURV

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

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: 20070129

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

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: 20061207

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

Ref country code: EE

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: 20060906

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: 20060906

Ref country code: LU

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

Effective date: 20070127

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

Ref country code: HU

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: 20070307

Ref country code: TR

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: 20060906

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

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

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20120509

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT SE SI SK TR

REG Reference to a national code

Ref country code: DE

Ref legal event code: R102

Ref document number: 60308071

Country of ref document: DE

Effective date: 20120509

REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Ref document number: 2271391

Country of ref document: ES

Kind code of ref document: T5

Effective date: 20120702

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

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

Ref country code: FR

Payment date: 20211217

Year of fee payment: 20

Ref country code: GB

Payment date: 20211209

Year of fee payment: 20

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

Ref country code: NL

Payment date: 20211216

Year of fee payment: 20

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

Ref country code: DE

Payment date: 20211130

Year of fee payment: 20

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

Ref country code: IT

Payment date: 20211213

Year of fee payment: 20

Ref country code: ES

Payment date: 20220203

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 60308071

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MK

Effective date: 20230126

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20230126

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20230410

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 EXPIRATION OF PROTECTION

Effective date: 20230128

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

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20230126