WO2008154572A2 - Use of hydrocarbon emulsions as a reburn fuel to reduce nox emissions - Google Patents
Use of hydrocarbon emulsions as a reburn fuel to reduce nox emissions Download PDFInfo
- Publication number
- WO2008154572A2 WO2008154572A2 PCT/US2008/066537 US2008066537W WO2008154572A2 WO 2008154572 A2 WO2008154572 A2 WO 2008154572A2 US 2008066537 W US2008066537 W US 2008066537W WO 2008154572 A2 WO2008154572 A2 WO 2008154572A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- emulsion
- furnace
- hydrocarbon
- fuel
- reburn
- Prior art date
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 86
- 229930195733 hydrocarbon Natural products 0.000 title claims description 45
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 42
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 42
- 239000000446 fuel Substances 0.000 title description 94
- 238000000034 method Methods 0.000 claims abstract description 75
- 239000010426 asphalt Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002485 combustion reaction Methods 0.000 claims abstract description 37
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003546 flue gas Substances 0.000 claims abstract description 17
- 238000002347 injection Methods 0.000 claims abstract description 17
- 239000007924 injection Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 239000010763 heavy fuel oil Substances 0.000 claims description 9
- -1 atmospheric residue Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 4
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 4
- 230000008569 process Effects 0.000 abstract description 40
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 32
- 230000009467 reduction Effects 0.000 description 20
- 238000006722 reduction reaction Methods 0.000 description 20
- 239000012530 fluid Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000003921 oil Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 238000000889 atomisation Methods 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 239000008346 aqueous phase Substances 0.000 description 8
- 238000010796 Steam-assisted gravity drainage Methods 0.000 description 7
- 239000000567 combustion gas Substances 0.000 description 7
- 230000009977 dual effect Effects 0.000 description 7
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 7
- 238000010531 catalytic reduction reaction Methods 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 229910052720 vanadium Inorganic materials 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000009434 installation Methods 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000010794 Cyclic Steam Stimulation Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 239000007764 o/w emulsion Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000016796 Euonymus japonicus Nutrition 0.000 description 1
- 240000006570 Euonymus japonicus Species 0.000 description 1
- 241000405425 Hura Species 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 239000002569 water oil cream Substances 0.000 description 1
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J7/00—Arrangement of devices for supplying chemicals to fire
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63C—LAUNCHING, HAULING-OUT, OR DRY-DOCKING OF VESSELS; LIFE-SAVING IN WATER; EQUIPMENT FOR DWELLING OR WORKING UNDER WATER; MEANS FOR SALVAGING OR SEARCHING FOR UNDERWATER OBJECTS
- B63C11/00—Equipment for dwelling or working underwater; Means for searching for underwater objects
- B63C11/52—Tools specially adapted for working underwater, not otherwise provided for
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/235—Heating the glass
-
- 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
- F23C6/00—Combustion apparatus characterised by the combination of two or more combustion chambers or combustion zones, e.g. for staged combustion
- F23C6/04—Combustion apparatus characterised by the combination of two or more combustion chambers or combustion zones, e.g. for staged combustion in series connection
- F23C6/045—Combustion 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
-
- 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
- F23C99/00—Subject-matter not provided for in other groups of this subclass
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23D—BURNERS
- F23D11/00—Burners using a direct spraying action of liquid droplets or vaporised liquid into the combustion space
- F23D11/10—Burners using a direct spraying action of liquid droplets or vaporised liquid into the combustion space the spraying being induced by a gaseous medium, e.g. water vapour
- F23D11/16—Burners using a direct spraying action of liquid droplets or vaporised liquid into the combustion space the spraying being induced by a gaseous medium, e.g. water vapour in which an emulsion of water and fuel is sprayed
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23D—BURNERS
- F23D14/00—Burners for combustion of a gas, e.g. of a gas stored under pressure as a liquid
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23K—FEEDING FUEL TO COMBUSTION APPARATUS
- F23K5/00—Feeding or distributing other fuel to combustion apparatus
- F23K5/02—Liquid fuel
- F23K5/08—Preparation of fuel
- F23K5/10—Mixing with other fluids
- F23K5/12—Preparing emulsions
-
- 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
- F23C2201/00—Staged combustion
- F23C2201/10—Furnace staging
- F23C2201/101—Furnace staging in vertical direction, e.g. alternating lean and rich zones
Definitions
- the invention relates to a method of reducing NO x emissions from various types of furnaces ranging from utility boilers to industrial package boilers to Once Through Steam Generators to refinery furnaces.
- Zamanshy et al . , USP 6,471,506, utilizes metal containing compounds in a furnace reburn zone to reduce NO x .
- Zauderer USP 6,453,830, reduces NO x by introducing sufficient fuel into the furnace downstream of the primary combustion zone into a fuel rich zone at a temperature that favors the conversion of NO x to N2. Then further downstream air is added to complete combustion of any unburned fuel.
- Additional fuel where the fuel is pyrolysis gas from the partial gasification of a solid fuel, is introduced into a downstream combustion zone as solid particles dispersed in aqueous droplets of varying size.
- the fuel is a liquid fuel or is pulverized coal or shredded biomass particles.
- a fuel rich zone is established containing a plurality of reduced n-containing species, introducing over fire air downstream of the fuel rich zone so that the n-containing species react with the NOX in the overfire zone.
- Hura et al . USP 5,908,003, burns a solid fuel in a primary zone and injects a gaseous fuel into a downstream fuel lean zone at a temperature of 1800 to 2400 0 F.
- Reburn is a combustion hardware modification in which the NO x produced in the main combustion zone is reduced downstream by providing a second combustion zone (the reburn zone) .
- a second combustion zone the reburn zone
- the reburn fuel is typically natural gas or micronized coal, a coal that is pulverized to 90% through a 300-mesh screen.
- the reburn fuel is injected into the furnace to create a fuel-rich zone where the NO formed in the main combustion zone is reduced to N 2 , NH 3 , HCN, other reduced nitrogen compounds and water vapor.
- the reburn fuel may be injected alone or may be injected with a carrying medium such as re-circulated flue gas to improve fuel distribution in the furnace.
- the gas reburn principal can be implemented in several ways.
- the traditional approach involves overall fuel-rich gas reburn. NO containing furnace gases from the primary combustion zone enter a downstream gas mixing and reburn zone in which a sufficient flow rate of natural gas is injected to form an overall fuel-rich mixture, Essentially, a region in the secondary combustion zone is driven sub-stoichiometric.
- the total fuel flow to the reburn zone of the furnace is typically in the range of 10% to 20% of the total energy input utilized in the furnace.
- Reburn reactions in the overall fuel-rich NO x reduction reburn zone reduce NO to N2, but produce relatively high levels of CO.
- Nitrogen in the reburn zone enters from the combustion gases from the primary combustion zone and from nitrogen contained in the reburn fuel, if any.
- This CO produced in the reburn zone is then reduced in a final burnout zone by injecting completion overfire air to produce overall lean conditions in which oxidation of the reburn gas is completed.
- completion overfire air to produce overall lean conditions in which oxidation of the reburn gas is completed.
- a related technology the modified reburn process, can achieve comparatively moderate NO x reductions, but at a much lower heat input than in conventional reburn furnaces, and without the need for a completion overfire air system to achieve CO burnout.
- natural gas or an emulsion of water and oil is injected into the upper furnace at sufficiently low rates to maintain overall fuel-lean conditions in the upper furnace region.
- the NO x reburning reactions then occur within local fuel-rich regions formed by the gas injection and the mixing process .
- the carrier gas maybe steam, air, or combustion products.
- Steam is expensive.
- air or recycled combustion products such as flue gas recirculation requires expensive ductwork, or the need for an expensive flue gas recirculation fan. These fans are expensive to operate and high maintenance items.
- Micronized coal requires a long burnout time when utilized as a reburn fuel. Utilizing micronized coal as a fuel source requires that both the fuel and the completion air be added at an earlier point in the furnace. As a result, much of the reaction occurs at higher temperatures, which results in more NO x emissions.
- EPRI Electric Power Research Institute
- Selected Catalytic Reduction can achieve lowest NOx emissions levels but create operational and maintenance problems that impact costs and boiler availability.
- Low NO x Burners alone can not achieve the low NOx levels alone without adding Over Fire Air as an example.
- Low NO x Burners' firing refinery gas can experience stability problems.
- Selected Non-Catalytic Reduction can not achieve low NOx levels (primary objective) and has high ammonia slip.
- Advanced oil recovery methods such as the Cyclic Steam Stimulation process (CSS) and the Steam Assisted Gravity Drainage (SAGD) process, use steam to extract oil in situ through the use of injected steam. Boilers used in these processes do not presently use reburn technology.
- a bitumen containing aqueous emulsion is injected into the flue gas of a furnace downstream of the primary combustion chamber and combusted in an oxygen poor reducing environment to remove a significant portion of the NOx components in the combustion gases.
- the emulsion is a hydrocarbon in water emulsion where the hydrocarbon component may itself be an emulsion of varying composition in the aqueous component of the emulsion .
- the aqueous component of the emulsion may be composed simply of water or may contain nitrogenous compounds such as urea or ammonia.
- the hydrocarbon component is preferably composed of bitumen, vacuum residue, or asphalt or a mixture thereof where the individual components of the hydrocarbon emulsion may vary greatly in proportion.
- the oil in water emulsion is injected into the secondary combustion region of the furnace above the primary combustion zone in a manner that creates oil in water bilayered droplets with an external aqueous layer of water alone or in combination with urea, or ammonia and an inner hydrocarbon layer of bitumen, vacuum residue or asphalt or mixture thereof.
- the droplets are evenly distributed throughout the input stream and not broken when the emulsion passes through the atomizer or injector into the furnace.
- the emulsion droplets are sized (Sauter Mean Diameter (SMD) by the atomizer/injector, so that the jet penetration and evaporation rate allow for the formation of localized fuel rich contrary currents.
- the droplets provide secondary atomization (micro-explosions) as the liquid aqueous outer droplet layer vaporizes to steam and releases the smaller hydrocarbon droplets which create localized fuel rich contrary currents.
- injectors that are in several planes of the furnace to cover a range of regions in the furnace .
- FIGURES Figure 1 is a conceptual diagram of the contrary current local cloud NO x reduction process in accordance with the present invention.
- Figure 2 is a process flow diagram, which shows the fuel handling and emulsion making process of the reburn fuel for delivery to the atomizers/injectors.
- Figure 3 is an example of a dual fluid atomizer/injector using either steam or sour solution gas as an atomizing fluid and the resultant primary and secondary atomization process used to both set up the localized fuel rich contrary currents and introduce the fixed reduced nitrogen agent in accordance with the present invention.
- Figure 4 is a diagram showing one embodiment of the fuel injector delivery system of the present invention.
- FIGS 5 & 6 are diagrams of a utility boiler and Once Through Steam Generator furnace to which injectors have been added in accordance with the present invention.
- NO x components in the combustion gases from a furnace are reduced by injecting a bitumen containing aqueous emulsion into the flue gas of a furnace downstream of the primary combustion chamber and combusted in an oxygen poor reducing environment to remove a significant portion of the NO x components in the combustion gases.
- sour gas solution means natural gas that is not refined and often contains species such as hydrogen sulfide (H 2 S) in the 2000PPM range.
- Atmospheric tower bottoms is the byproduct that remains and reflects the fraction or cut of the refining distillation curve representing products with a boiling temperature >800°F (>426.7°C) .
- vacuum residue means the fraction that remains after distillation of bitumen or crude oil under either atmospheric (ATB or Atmospheric Tower Bottom) or vacuum (VTB or Vacuum Tower Bottom) conditions that contains fewer volatiles.
- Straight run residue or ATB is a byproduct that remains and reflects the fraction or cut of the refining curve representing products with a boiling temperature greater than or equal to 800 0 F (426.7°C).
- the typical application of this bottom product (VTB) is feed to an asphalt plant, a thermal cracker, a coker, or as a blending component for residual fuel (#6 HFO) .
- Asphalt is one of two available alternatives the refiner or upgrading process may consider for these bottom residues, depending upon the quality of the bitumen and the available market .
- Asphaltene concentration determines the quality of the asphalt.
- Asphaltenes are very complex molecular substances found naturally in neat bitumen, which impart a high viscosity to the residue appearing solid at room temperature.
- Asphaltenes consist of polyaromatic compounds with high carbon-to-hydrogen ratios (-1:1.2 depending on source) defined operationally as the n-heptane insoluble, toluene soluble component of carbonaceous material, such as crude oil or bitumen.
- Solvent De-Asphalter is the next step along the refining process, which operates at an even higher temperature to handle an even more viscous product.
- the SDA process uses a hydrocarbon solvent tailored to ensure the most economical de-asphalting design.
- Propane solvent is typical for the low-de-asphalted oil or a heavier residue or bitumen. Designs have been developed to produce a maximum yield of de-asphalted oil and minimum yield of asphalt, the latter having a viscosity range of 60,000 cp at 530 0 F (276.7 0 C) with a very high concentration of asphaltene.
- bitumen means a mixture of highly viscous primarily highly condensed polycyclic aromatic hydrocarbons.
- Naturally occurring or crude bitumen is a sticky, tar-like form of petroleum. Refined bitumen is obtained by fractional distillation of crude oil. It is the heaviest fraction and the one with the highest boiling point, boiling at 525 0 C (977 0 F) .
- Most bitumens contain sulfur and several heavy metals such as nickel, vanadium, lead, chromium, mercury and also arsenic, selenium, and other toxic elements.
- Naturally occurring crude bitumen is the prime feed stock for petroleum production from oil sands currently under development in Alberta, Canada. Canada has most of the world's supply of natural bitumen.
- the Athabasca oil sands is the largest bitumen deposit in Canada and the only one accessible to surface mining, although recent technological breakthroughs have resulted in deeper deposits becoming producible by in-situ methods.
- nitrogen bitumen is a product extracted from oil sands (typically using the SAGD or CSS process) , is very viscous and is also referred to as non- conventional oil or crude bitumen to distinguish it from the freer-flowing hydrocarbon mixtures.
- burnout air or "overfire air” means the air introduced to the furnace downstream of the reburn zone to complete combustion in a burnout zone downstream of the reburn zone
- the fuel utilized in all embodiments of the invention comprises an emulsion of a hydrocarbon and water.
- the emulsion may be an oil in water emulsion or a water in oil emulsion.
- the two types of emulsions function differently in the instant process.
- the hydrocarbon component may itself be an emulsion of varying composition in the aqueous component of the emulsion .
- the droplet size is an important characteristic and may range in diameter from 60 to 300 micrometer or larger encasing 5 to 30 micrometers of inner droplet, preferably from 60 to 300 micrometer encasing 5 to 20 micrometers of inner droplet.
- the aqueous component of the emulsion may be composed simply of water or may contain nitrogenous compounds such as urea or ammonia.
- the instant process will allow the water to volatilize first and result in the process chemistry to take place in the fuel rich clouds (local sub- stoichiometric air to fuel ratios) created by the small droplets of hydrocarbons from the inner bilayer of the fuel droplets released by the secondary atomization process .
- the emulsion comprises an aqueous phase comprising from 1% to 32% of the total volume (1 to 43% by weight) of the droplet, preferably 20% to 32% by volume (30 to 43% by weight) , most preferably 15% to 25% by volume (20 to 34% by weight) .
- the oil in water emulsions usable comprise 5 to 25, preferably 5 to 20 micron size hydrocarbon droplets (SMD) in larger (80 to 300 micron) water droplets.
- SMD micron size hydrocarbon droplets
- the size of the hydrocarbon droplets which form the center portion of the water droplets is determined by the process by which the emulsion is formed and by the micro explosions of the vaporized aqueous surface of the droplets that serves to disperse the hydrocarbons.
- the injector and/or atomizer is the delivery system that distributes the 80 to 300 micron droplets of the oil in water emulsion to the furnace (primary atomization) .
- the water in oil emulsions usable comprise 80 to 300 micron size hydrocarbon droplets (SMD) established by the injector and/or atomizer (primary atomization) with the size of the smaller water droplets encompassed within the droplet determined by the emulsion process and are typically in the range of 5 to 30 microns or larger dispersed in the oil emulsion droplets.
- SMD micron size hydrocarbon droplets
- the percentage of water in oil in water emulsions is in the range of about 10 to 32% with optimum percentage water in the 20 to 30% range.
- the percentage of water in water in oil emulsions is in the range of about 1 to 10% with the optimum percentage water in the 5 to 8% range.
- the emulsion can also be made from a urea solution or aqueous ammonia solution where the normal stoichiometric ratio (NSR) which defines the concentration of the solution (amount of urea, etc.) based on the amount of NO x emissions exiting the primary flame zone is between 1 and 3.
- NSR normal stoichiometric ratio
- the aqueous phase of the droplets provides a means of control of the reaction temperature in the fuel rich zones, which will improve the NO x removal.
- the hydrocarbon component is preferably composed of bitumen, atmospheric residue, heavy fuel oil, vacuum residue, asphalt, or solvent de-asphalter or a mixture thereof where the individual components of the hydrocarbon emulsion may vary greatly in proportion.
- the amount of the hydrocarbon component in the hydrocarbon emulsion is as follows:
- Bitumen 57 to 99%, preferably 60 to 85%, most preferably 65 to 80% by weight.
- Atmospheric residue 57 to 99%, preferably 60 to 85%, most preferably 65 to 80% by weight.
- Heavy fuel oil 57 to 99%, preferably 60 to 85%, most preferably 65 to 80% by weight.
- Vacuum Residue 57 to 99%, preferably 60 to 85%, most preferably 65 to 80% by weight.
- Asphalt 57 to 99%, preferably 60 to 85%, most preferably 65 to 80% by weight.
- Solvent de-asphalter 57 to 99%, preferably 60 to 85%, most preferably 65 to 80% by weight.
- the hydrocarbon emulsion of bitumen, atmospheric residue, heavy fuel oil, vacuum residue, asphalt, or solvent de-asphalter is produced by providing high shear to the materials as shown in Figure 2.
- the mixture of hydrocarbons forms an emulsion in which the bitumen, vacuum residue (VTB and SDA) , or asphalt droplets are small enough so that a majority of them do not break or coalesce when the emulsion is stored in a day tank or passes through the atomizer/injector into the furnace.
- the emulsion of water (only or fixed nitrogen enhanced water) and hydrocarbon is introduced into the boiler after the primary combustion zone in a region where the temperature is in the range of about 2000 0 F to 2600 0 F or about 1100°C to 1427°C, as shown in Figure 1.
- the emulsion is injected into regions of the furnace in which the flue gas temperature is between 1900 0 F (1038°C) and 2600 0 F (1427°C), preferably between 1900°F (1038 0 C) and 2350°F (1288°C), most preferably between 1900 0 F (1038°C) and 2200°F (1205 0 C) .
- the process is designed to allow the disclosed reburn fuel to react with the oxygen in the reburn combustion process and to burn out almost completely.
- the volatization of the hydrocarbons present in the hydrocarbon phase is delayed while the water volatilizes.
- the delay may be finely tuned to the type of furnace and combustion conditions so as to achieve and maintain a desired temperature in the secondary combustion, region to maximize NO x removal consistent with the maintenance of other suitable operating conditions. This procedure results in the lowest possible emissions of NO x at the lowest cost.
- emulsion is made from materials that are less expensive than the base fuel
- higher quantities of heat inputs of reburn fuel may be used to achieve higher NOx reductions .
- the temperature window of the presently described process is much wider than other reburn and Selected Non- Catalytic Reduction (SNCR) processes.
- the temperature window is 19000F (1038 0 C) to 2600oF (1427°C) .
- the emulsion is from 5% to 32%, preferably 20 to 30% aqueous phase and adjustments can be made to accommodate different furnaces or furnace conditions.
- the emulsion is injected into fuel rich areas (sub- stoichiometric conditions) of the furnace and the secondary atomization and water volatization takes place in the localized fuel rich regions.
- the ratio of aqueous phase to hydrocarbon phase in the droplets may be modified to provide an aqueous phase within the range of 5% to 34% to further modify the very local reburn temperature.
- the heat input from these emulsified fuels is between 1% and 20% of the total boiler heat input. In a preferred embodiment, the heat input from these emulsified fuels is between 2% and 7.9%. Most preferably the heat input from these emulsified fuels is between 5% and 7%.
- the droplet has an outside diameter in the range of 60 to 300 microns or larger, preferably 80 to 300 micron, most preferably 120 to 300 micron.
- the oleophilic inner droplet layer has a diameter of from 5 to 25 micron, preferably 6 to 20 micron, most preferably 6 to 15 micron droplets.
- the reburn reaction takes place in the fuel rich contrary currents of the furnace zone down stream of (see attached figures for injection locations) the primary flame zone .
- aqueous phase of the emulsion contains urea or aqueous ammonia
- an additional NO x reduction is obtained from the secondary atomization characteristics of the emulsion releasing the fixed reduced nitrogen agents in the fuel rich contrary currents or the deep staged regions of the primary flame zone prior to the introduction of overfire air.
- overfire air can be used in the instant process the preferred method is not to use overfire air.
- the instantly disclosed method allows for lower NSR and the least amount of ammonia slip.
- CO burnout is achieved by the excess oxygen available in the fuel gas from the primary flame zone, without the need for a completion overfire air system (OFA) or in the deep staged condition with the introduction of OFA.
- OFA completion overfire air system
- the emulsion is introduced both as streams (jets) and spray droplets, usually in combination to assure better coverage .
- Figure 3 shows an example of a single "Y" jet dual fluid atomizer providing primary atomization using the energy from the atomizer and secondary atomization from the emulsion to both release the fixed nitrogen reagent and create the fuel rich local cloud (contrary currents).
- a low-pressure mechanical atomizer can be used to inject the emulsion into the furnace.
- Preferred methods of introducing the burnout fuel utilize either dual fluids using sour solution gas or low pressure (100 to 250 PSI range) mechanical injectors. The most preferred injection method utilizes low pressure (125 to 200 PSI range) mechanical injectors.
- Sour solution gas is a preferred atomizing fluid in the atomizers/injectors.
- Other atomizing fluids such as steam may be used.
- the ratio of sour solution gas or steam to emulsion product in the atomizers/injectors is in the range of 0.05:1 to 0.5:1 atomizing fluid to emulsion product, preferably in the range of 0.05:1 to 0.20:1, most preferably in the range of 0.05:1 to 0.10:1 of sour solution gas or steam to the emulsion (on a pound per pound basis of atomizing fluid to fuel) .
- low pressure mechanical injectors requiring no atomizing fluid are utilized.
- the chemistry of the process is complex and involves over thirty (30) chemical reactions.
- the process can be represented by one (1) basic equation which occurs in a localized reducing atmosphere at a temperature in the range of about 1100 0 C and 1425°C: NO x + NH 3 + H 2 O + H 2 ⁇ N 2 + H 2
- hydrocarbon radicals are produced due to the pyrolysis of the fuel in an oxygen-deficient, high temperature environment.
- the hydrocarbon radicals then mix with the combustion gases from the main combustion zone and react with NO to form CN radicals, NH 2 radicals, and other stable products (Equations 3.1.1-2 to 3.1.1-4).
- the excess air (O 2 ) from the primary flame zone is used to complete the fuel burnout after the local reburn zones have reduced the NOx emissions. Conversion of HCN and ammonia compounds in the burnout zone may regenerate some of the decomposed NO,, by the reactions.
- the bilayer emulsion is preferably introduced through atomizing nozzles or injectors, which can handle the bilayer emulsion without breaking it down, and through jets for maximum penetration and optimum droplet size distribution .
- the atomizers can include internal mixing, "Y" jet, and “F” jet dual fluid atomizers with a range of spray angles, including cone shaped spray angles, flat sprays, individual finger sprays and single jet sprays.
- These dual fluid atomizers can use various atomizing fluids with either steam or sour solution gas as the preferred atomizing fluid and sour solution gas as the most preferred atomizing fluid.
- the ratio of atomizing fluid to emulsion product can range from 0.05:1 to 0.5:1 preferably from 0.05:1 to 0.20:1, most preferably from 0.05:1 to 0.10:1.
- Operating pressures may range from 20 PSIG to 150 PSIG, preferably from 75 to 125, most preferably from 100 to 125 for dual fluid injectors.
- the preferred injection method utilizes either dual fluids using sour solution gas or low pressure (100 to 250 PSI range) mechanical injectors.
- the most preferred injection method utilizes low pressure (125 to 200 PSI range) mechanical injectors.
- reburn fuel droplets are delivered to the total furnace reburn region.
- the reburn area the area of the furnace where the furnace atmosphere is a reducing atmosphere
- the reburn fuel is injected with the reburn fuel without mixing any of the reburn fuel into other areas of the furnace where the oxidizing atmosphere is left unchanged.
- Figure 4 shows an example of a multi-nozzle fuel handling and delivery system to be used to inject the emulsion products into the furnace at several furnace planes, levels, and areas.
- no burnout air is used and a face fired or opposed fired utility boiler is used it is preferred to establish where the lanes of reducing mixtures are located and inject the reburn emulsion into these lanes while maintaining oxidizing lanes between the injection lanes.
- the relative width of the lanes depends upon the amount of oxygen in the initial combustion products, the final amount of oxygen, and how much additional fuel will be injected into the reducing lanes.
- the absolute widths will be sufficient to allow almost complete volatilization and combustion of the hydrocarbon reburn fuel in the reducing zone.
- the evaporation of the urea and/or aqueous ammonia, if present in the emulsion, takes place in these reducing lanes, thus allowing for the fixed nitrogen reagent to be activated in these reducing lanes.
- the NO x ' s present are treated in the furnace after the combustion gases have exited the cyclones.
- a lane arrangement is best unless completion air is used.
- OTSG Once Through Steam Generator
- a package drum boiler a field erected industrial boiler/furnace or a horizontal pass type "D" package boiler
- OTSG Once Through Steam Generator
- a package drum boiler a field erected industrial boiler/furnace or a horizontal pass type "D" package boiler
- streams of reburn fuel emulsion into lanes of reducing mixtures established by the primary burner/atomizer (fingers of fuel rich fuel), by injecting the emulsion into these lanes and maintaining oxidizing lanes between these lanes.
- the relative width of the lanes depends upon the amount of oxygen in the initial combustion products, the final amount of oxygen, and how much surplus fuel is to be in the reducing lanes.
- the same general arrangement of reburn fuel emulsion injection is used with or without completion air.
- Circulating Fluidized Bed (CFB) boiler where no burnout air is used
- the relative width of the lanes depends upon the amount of oxygen in the initial combustion products, the final amount of oxygen, and how much surplus fuel is to be in the reducing lanes.
- the same general arrangement of reburn fuel emulsion injection is used with and without completion air.
- Figures 5 & 6 show examples of the reburn injection without completion air in both a Once Through Steam Generator and a face fired utility boiler.
- the inventive process does not require carrier air, steam, or re-circulated flue gas.
- the atomizing fluid is preferably sour solution gas used at heat inputs ranging from 0.35% to 2% of the total heat input of the boiler.
- expected NOx reductions can range from 25% to 65% of the total NO x exiting the primary flame zone .
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002688141A CA2688141A1 (en) | 2007-06-11 | 2008-06-11 | Use of hydrocarbon emulsions as a reburn fuel to reduce nox emissions |
GB0921727.4A GB2462772B (en) | 2007-06-11 | 2008-06-11 | Use of hydrocarbon emulsions as a reburn fuel to reduce NOx emissions |
US12/632,255 US20100116183A1 (en) | 2007-06-11 | 2009-12-07 | Use of hydrocarbon emulsions as a reburn fuel to reduce nox emissions |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US94313307P | 2007-06-11 | 2007-06-11 | |
US60/943,133 | 2007-06-11 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US12/632,255 Continuation US20100116183A1 (en) | 2007-06-11 | 2009-12-07 | Use of hydrocarbon emulsions as a reburn fuel to reduce nox emissions |
Publications (2)
Publication Number | Publication Date |
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WO2008154572A2 true WO2008154572A2 (en) | 2008-12-18 |
WO2008154572A3 WO2008154572A3 (en) | 2009-02-26 |
Family
ID=40130478
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/US2008/066537 WO2008154572A2 (en) | 2007-06-11 | 2008-06-11 | Use of hydrocarbon emulsions as a reburn fuel to reduce nox emissions |
Country Status (4)
Country | Link |
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US (1) | US20100116183A1 (en) |
CA (1) | CA2688141A1 (en) |
GB (1) | GB2462772B (en) |
WO (1) | WO2008154572A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103776052A (en) * | 2014-02-12 | 2014-05-07 | 重庆紫光新科化工开发有限公司 | Control method and control system for combustion temperature of low calorific value gas |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105733730A (en) * | 2016-02-04 | 2016-07-06 | 黑龙江泰昇农业科技开发有限公司 | Biomass micron carbonized power high-temperature combustion method |
CN108488784B (en) * | 2018-01-30 | 2020-10-02 | 中国神华能源股份有限公司 | Pulverized coal combustion boiler system and pulverized coal combustion boiler operation method |
CN112628725B (en) * | 2021-01-12 | 2021-11-12 | 哈尔滨工业大学 | Radial grading low NOx pulverized coal combustion device |
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US5756059A (en) * | 1996-01-11 | 1998-05-26 | Energy And Environmental Research Corporation | Advanced reburning methods for high efficiency NOx control |
US5890442A (en) * | 1996-01-23 | 1999-04-06 | Mcdermott Technology, Inc. | Gas stabilized reburning for NOx control |
US20030079665A1 (en) * | 2001-11-01 | 2003-05-01 | Arvind Atreya | Furnace having increased energy efficiency and reduced pollutant formation |
US6694900B2 (en) * | 2001-12-14 | 2004-02-24 | General Electric Company | Integration of direct combustion with gasification for reduction of NOx emissions |
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JPS5121016A (en) * | 1974-08-13 | 1976-02-19 | Nissan Motor | Nohakukongokikyokyugatanainenkikanno haikijokasochi |
US3986669A (en) * | 1976-03-23 | 1976-10-19 | Martner John G | Ultrasonic tubular emulsifier and atomizer apparatus and method |
US4325924A (en) * | 1977-10-25 | 1982-04-20 | Electric Power Research Institute, Inc. | Urea reduction of NOx in fuel rich combustion effluents |
US4203759A (en) * | 1978-05-01 | 1980-05-20 | Exxon Research & Engineering Co. | Process for the preparation of a vanadium-containing metallic ash concentrate |
US6481998B2 (en) * | 1995-06-07 | 2002-11-19 | Ge Energy And Environmental Research Corporation | High velocity reburn fuel injector |
US5908003A (en) * | 1996-08-15 | 1999-06-01 | Gas Research Institute | Nitrogen oxide reduction by gaseous fuel injection in low temperature, overall fuel-lean flue gas |
US5967061A (en) * | 1997-01-14 | 1999-10-19 | Energy And Environmental Research Corporation | Method and system for reducing nitrogen oxide and sulfur oxide emissions from carbonaceous fuel combustion flue gases |
US6213032B1 (en) * | 1999-08-30 | 2001-04-10 | Energy Systems Associates | Use of oil water emulsion as a reburn fuel |
US6206685B1 (en) * | 1999-08-31 | 2001-03-27 | Ge Energy And Environmental Research Corporation | Method for reducing NOx in combustion flue gas using metal-containing additives |
US6453830B1 (en) * | 2000-02-29 | 2002-09-24 | Bert Zauderer | Reduction of nitrogen oxides by staged combustion in combustors, furnaces and boilers |
US6357367B1 (en) * | 2000-07-18 | 2002-03-19 | Energy Systems Associates | Method for NOx reduction by upper furnace injection of biofuel water slurry |
US6968791B2 (en) * | 2003-08-21 | 2005-11-29 | Air Products And Chemicals, Inc. | Oxygen-enriched co-firing of secondary fuels in slagging cyclone combustors |
US7168947B2 (en) * | 2004-07-06 | 2007-01-30 | General Electric Company | Methods and systems for operating combustion systems |
US7497172B2 (en) * | 2005-10-12 | 2009-03-03 | Breen Energy Solutions | Method to decrease emissions of nitrogen oxides and mercury through in-situ gasification of carbon/water slurries |
-
2008
- 2008-06-11 WO PCT/US2008/066537 patent/WO2008154572A2/en active Application Filing
- 2008-06-11 CA CA002688141A patent/CA2688141A1/en not_active Abandoned
- 2008-06-11 GB GB0921727.4A patent/GB2462772B/en active Active
-
2009
- 2009-12-07 US US12/632,255 patent/US20100116183A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5756059A (en) * | 1996-01-11 | 1998-05-26 | Energy And Environmental Research Corporation | Advanced reburning methods for high efficiency NOx control |
US5890442A (en) * | 1996-01-23 | 1999-04-06 | Mcdermott Technology, Inc. | Gas stabilized reburning for NOx control |
US20030079665A1 (en) * | 2001-11-01 | 2003-05-01 | Arvind Atreya | Furnace having increased energy efficiency and reduced pollutant formation |
US6694900B2 (en) * | 2001-12-14 | 2004-02-24 | General Electric Company | Integration of direct combustion with gasification for reduction of NOx emissions |
Cited By (1)
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CN103776052A (en) * | 2014-02-12 | 2014-05-07 | 重庆紫光新科化工开发有限公司 | Control method and control system for combustion temperature of low calorific value gas |
Also Published As
Publication number | Publication date |
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GB0921727D0 (en) | 2010-01-27 |
GB2462772B (en) | 2012-10-10 |
US20100116183A1 (en) | 2010-05-13 |
WO2008154572A3 (en) | 2009-02-26 |
GB2462772A (en) | 2010-02-24 |
CA2688141A1 (en) | 2008-12-18 |
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