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WO2008002290A1 - systÈmes de contrÔle d'Émissions et LEURS procÉdÉs - Google Patents

systÈmes de contrÔle d'Émissions et LEURS procÉdÉs Download PDF

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Publication number
WO2008002290A1
WO2008002290A1 PCT/US2006/024835 US2006024835W WO2008002290A1 WO 2008002290 A1 WO2008002290 A1 WO 2008002290A1 US 2006024835 W US2006024835 W US 2006024835W WO 2008002290 A1 WO2008002290 A1 WO 2008002290A1
Authority
WO
WIPO (PCT)
Prior art keywords
ammonia
exhaust emission
delivery system
set forth
exhaust
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.)
Ceased
Application number
PCT/US2006/024835
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English (en)
Inventor
Joe W. Cochran
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.)
Progress Materials Inc
Original Assignee
Progress Materials Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Progress Materials Inc filed Critical Progress Materials Inc
Priority to PCT/US2006/024835 priority Critical patent/WO2008002290A1/fr
Publication of WO2008002290A1 publication Critical patent/WO2008002290A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/026—Preparation of ammonia from inorganic compounds
    • C01C1/028—Preparation of ammonia from inorganic compounds from ammonium sulfate or sulfite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/24—Sulfates of ammonium
    • C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia

Definitions

  • This invention generally relates to systems and methods for emissions control and, more particularly, to nitrogen oxide and sulfur trioxide emission control systems and methods thereof.
  • Exhaust emission from coal fired furnaces or boilers such as those used in power plants may contain a variety of different gases depending on the type of coal being burned.
  • the amounts at which some of these gases could be emitted into the environment are regulated. For example, there are restrictions on the amount of nitrogen oxides which could be emitted into the atmosphere.
  • a method for controlling one or more emissions in accordance with embodiments of the present invention includes introducing ammonia to react with at least a portion of sulfur trioxides in an exhaust emission and results in at least one or more ammoniated compounds. At least a portion of fly ash particles and the ammoniated compounds in the exhaust emission are precipitated. At least a portion of the ammonia from the precipitated ammoniated compounds is recovered with heat from the exhaust emission and the recovered ammonia is reused.
  • a system for controlling one or more emissions in accordance with other embodiments of the present invention includes a first ammonia delivery system, the precipitator system, the recovery system, and the resupply system.
  • the first ammonia delivery system is connected to an exhaust system to introduce ammonia that reacts with at least a portion of sulfur trioxides in an exhaust emission and results in at least one or more ammoniated compounds.
  • the precipitator system precipitates at a least a portion of fly ash particles and the ammoniated compounds in the exhaust emission.
  • the recovery system recovers at least a portion of the ammonia from the precipitated ammoniated compounds with heat from the exhaust emission.
  • the resupply system supplies the recovered ammonia to the first ammonia delivery system.
  • a method for making a system for controlling one or more emissions in accordance with other embodiments of the present invention includes connecting a first ammonia delivery system to an exhaust system to introduce ammonia that reacts with at least a portion of sulfur trioxides in an exhaust emission and results in at least one or more ammoniated compounds.
  • a precipitator system is connected to the exhaust system to precipitate at a least a portion of fly ash particles and the ammoniated compounds in the exhaust emission.
  • a recovery system is connected to the precipitator system and the exhaust system that recovers at least a portion of the ammonia from the precipitated ammoniated compounds with heat from the exhaust emission.
  • a resupply system is connected to the first ammonia delivery system that supplies the recovered ammonia.
  • the present invention provides a number of advantages including providing an effective system and method for controlling and reducing nitrogen oxides and sulfur trioxides in exhaust emission while recovering ammonia used to control these emissions. Additionally, the fly ash particles, from which the ammonia is recovered, could be used for other applications, such as a substitute for a portion of the cement in concrete.
  • the present invention provides a system in which NH3 injection could be used for its very effective control of nitrogen oxides and also control of blue plume (along with partial capture of sulfur compounds from the exhaust gases). Additionally, the present invention is able to achieve this control by utilizing the high concentrations of ammonia necessary to avoid creating problems in downstream power plant equipment, but without the large increase in ammonia cost and without contaminating the resulting fly ash such that it cannot be beneficially used. Further, the present invention accomplishes this without creating substantial new emissions, such as the conversion of ammoniated compounds into oxides of nitrogen.
  • FIG. 1 is a block diagram of an emission control system in accordance other embodiments of the present invention. DETAILED DESCRIPTION
  • the emission control system 10 includes an exhaust system 12, a selective catalytic reactor 14 (SCR), heat exchangers 16 and 18, ammonia injection systems 20 and 22, an electrostatic precipitator 24 (ESP), an ammonia recovery system 26, and a collection bin 28, although the sulfur emission control system 10 can comprise other numbers and types of components in other configurations.
  • the present invention provides an effective system and method for controlling and reducing nitrogen oxides and sulfur trioxides and for recapturing and reusing at least a portion of the injected ammonia used in reducing these emissions.
  • the exhaust system 12 comprises a number of lines, ducts or pipes 30(l)-30(6) and a chamber 32 which are used to transport and process the exhaust emission, although the exhaust system 12 can comprise other types and numbers of vessels for carrying and processing the exhaust emissions in other configurations.
  • the line 30(1) of the exhaust system 12 is connected to the exhaust emission outlet of a coal power plant furnace 15, although the exhaust system 12 could be connected to other sources of exhaust emission, such as to a coal fired industrial furnace.
  • the exhaust emission from the coal power plant 15 or other exhaust emission source which is input to the line 30(1) of the exhaust system 12 includes fly ash particles and one or more other gases, such as sulfur dioxides and nitrogen oxides, although the exhaust emission could include other elements.
  • the heat exchanger 16 (called an economizer in a coal fired power plant or similar boiler) is connected between the line 30(1) from the coal power plant furnace 15 and the line 30(2) to the selective catalytic reactor 14, although the heat exchanger 16 could be connected to other components and in other configurations.
  • the heat exchanger 16 reduces the temperature of the exhaust emission to between about 600 degrees to 750 degrees Fahrenheit which is a more optimal temperature for the removal of at least a portion of the nitrogen oxides in the selective catalytic reactor 14, although the temperature of the exhaust emission could be reduced to other temperatures.
  • the selective catalytic reactor 14 is connected between the line
  • an air preheater in a coal fired power plant or similar boiler although the selective catalytic reactor 14 could be connected to other components and in other configurations.
  • An ammonia injection system 20 is connected to and injects the ammonia (NH 3 ) into the selective catalytic reactor 14 which is used to react with and reduce the amount of nitrogen oxides in the exhaust emission. More specifically, the selective catalytic reactor 14 uses ammonia (NH 3 ) to reduce nitrogen oxides (NO ⁇ ) in the exhaust emission to nitrogen (N) and water (H 2 O) in a chemical reduction.
  • this reaction can be illustrated by the following generalized formula:
  • the catalytic action of the selective catalytic reactor 14 also causes a portion of the sulfur dioxide (SO 2 ) in the exhaust emission to react with oxygen to generate sulfur trioxide (SO 3 ) as illustrated in the following generalized formula:
  • Heat exchanger 18 which, as noted above, is called an air preheater in a coal fired power plant or similar boiler, is connected in the exhaust system 12 between the line 30(3) from the selective catalytic reactor 14 and the line 30(4) in the chamber 32, although the heat exchanger 18 could be connected to other components and in other configurations.
  • the heat exchanger 18 reduces the temperature of the exhaust emission to between about 275 degrees to 300 degrees Fahrenheit which is a more optimal temperature for the removal of at least a portion of the sulfur trioxides in the exhaust emission, although the temperature of the exhaust emission could be reduced to other temperatures.
  • the chamber 32 is connected in the exhaust system 12 between the line 30(4) from the heat exchanger 18 and the line 30(5) to the electrostatic precipitator 24, although the chamber 32 could be connected to other components in other configurations.
  • the ammonia injection system 22 is connected to and used to inject the ammonia into the chamber 32, although other manners for supplying ammonia could be used.
  • At least a portion of the sulfur trioxides react with the ammonia in the chamber 32 to form primarily ammonium sulfate and ammonium bisulfate, although other ammoniated compounds may be formed in smaller quantities and the mixing and reacting can take place in other types of vessels and in other locations.
  • ammonium bisulfate particles which are sticky, adhere to the fly ash particles while ammonium sulfate particles, which are dry solids, may be separate from, but mixed with, the fly ash particles.
  • the electrostatic precipitator 24 is connected between the line
  • the electrostatic precipitator 24 also is connected to supply precipitated fly ash particles (with the included ammoniated compounds) by a pipe 33 to the ammonia recovery system 26, although the electrostatic precipitator 24 could be connected to other components and in other configurations.
  • the electrostatic precipitator 24 is used to precipitate at least a portion of the fly ash particles and the ammoniated compounds from the exhaust emission, although other manners for separating the fly ash particles from the exhaust emission, such as baghouses, cyclones and wet electrostatic precipitators could be used.
  • the ammonia recovery system 26 includes a chamber 27 with gas mixing system 36, although the ammonia recovery system 26 can comprise other types and numbers of components.
  • the chamber 27 with the gas mixing system 36 is connected to receive the precipitated fly ash particles via the pipe 33 from the electrostatic precipitator 24, although the ammonia recovery system 26 could be connected to other components and in other configurations including, for example, intermediate fly ash storage and transport systems.
  • the gas mixing system 36 for the ammonia recovery system 26 is connected to receive hot gas from either just upstream of heat exchanger 18 via lines 38(1) and 38(3) or, optionally, from just upstream of heat exchanger 16 via lines 38(2) and 38(3).
  • the ammonia recovery system 26 also has outputs connected to a collection bin 28 in which the processed fly ash particles are collected and to pipes 40(l)-40(3) which return recovered ammonia along with the now cooler gas and small quantities of the fly ash back to the ammonia injection systems 20 and 22, although the outputs from the ammonia recovery system 26 could be connected to other components and in other configurations.
  • the stream in pipes 40(l)-40(3) could be routed through a cyclone or similar dust collection system to return the small amounts of fly ash to collection bin 28 and avoid recirculating it through the ammonia injection systems 20 and 22.
  • the ammonia recovery system 26 is used to recover at least a portion of the ammonia injected into the exhaust emission by the ammonia injection systems 20 and 22 during the reduction of nitrogen oxides and sulfur trioxides.
  • the ammonia injection systems 20 and 22 provide for injection of the recovered ammonia in a gaseous stream in addition to injection of liquid or vaporized fresh ammonia through typical SCR nozzles, although the ammonia injection systems 20 and 22 could introduce ammonia in one or more other manners.
  • Pulverized coal particles are combusted in the coal fired furnace 15 and the exhaust emission from this combustion is output into the line 30(1) of the exhaust system 12, although the exhaust emission could be provided by other sources and could be output in other manners.
  • the exhaust emission includes fly ash particles and one or more other gases, such as sulfur dioxides and nitrogen oxides, although the exhaust emission could include other elements.
  • the exhaust emission which is above about 750 degrees, is input to the heat exchanger 16 via line 30(1) where the temperature of the exhaust emission is reduced to between about 600 degrees to 750 degrees Fahrenheit to be at a more optimal temperature for the removal of at least a portion of the nitrogen oxides in the selective catalytic reactor 14, although the temperature of the exhaust emission could be reduced to other temperatures.
  • the exhaust emission is provided via line 30(2) to the selective catalytic reactor 14.
  • ammonia (NH 3 ) is supplied from the ammonia injection system 20 to the selective catalytic reactor 14, although other manners for reducing the nitrogen oxides could be used.
  • the ammonia (NH 3 ) in the selective catalytic reactor 14 converts at least a portion of the nitrogen oxides to nitrogen (N) and water (H 2 O) in a chemical reduction in the selective catalytic converter 14.
  • the partial recovery and reuse of ammonia enables the ammonia injection system 20 to more economically reduce more of the nitrogen oxides than was previously possible.
  • sulfur dioxide and oxygen which are also present in the exhaust emission, react in the presence of the catalyst in the selective catalytic reactor 14 to generate sulfur trioxide (SO 3 ).
  • SO 3 sulfur trioxide
  • the amount of sulfur dioxide in the exhaust emission depends on the amount of sulfur in the coal which was combusted and produced the exhaust emission.
  • the temperature of the exhaust emission leaving the selective catalytic reactor 14 is further reduced to a temperature between about 275 degrees to 300 degrees Fahrenheit to be at a more optimal temperature for the removal of at least a portion of the sulfur trioxides in the exhaust emission, although the temperature of the exhaust emission could be adjusted to other temperatures.
  • the exhaust emission is provided via line 30(4) to the chamber 32. Additionally, ammonia is provided to the chamber 32 from the ammonia injection system 22, although other manners and configurations could be used.
  • the ammonia supplied by the ammonia injection system 22 reacts with at least a portion of the sulfur trioxides which causes the reacted sulfur trioxides to form ammoniated compounds that adhere and/or are mixed in with the fly ash particles.
  • the ammonia is introduced by the ammonia injection system 22 at a rate and amount which results in a majority of these ammoniated compounds comprising ammonium sulfate particles, although the ammonia can be introduced at other rates and amounts. Additionally, the amount of ammonia supplied by the ammonia injection system 22 to the exhaust emission in the chamber 32 is greater than the amount of ammonia supplied by the ammonia injection system 20 to the exhaust emission in the selective catalytic reactor 14.
  • the amount of ammonia supplied by ammonia injection system 22 is about ten times the amount supplied by the ammonia injection system 20 to obtain the desired conversion of at least a portion of the sulfur trioxides, although other ratios of supplied ammonia by the respective ammonia injection systems 20 and 22 could be used.
  • the fly ash particles with the included ammoniated compounds are supplied via line 30(5) to the electrostatic precipitator 24 where they are at least partially precipitated out of the exhaust emission, although other manners for separating the fly ash particles and ammoniated compounds from the exhaust emission could be used.
  • the precipitated fly ash particles are supplied via a pipe 33 to the chamber 27 of the ammonia recovery system 26, although the precipitated fly ash particles could be supplied to other locations and in other manners.
  • Hot exhaust emission gas taken from either line 30(3) after the selective catalytic reactor 14 or line 30(1) before the heat exchanger 16 is routed to the gas mixing system 36 via either lines 38(1) and 38(3) or 38(2) and 38(3).
  • the gas mixing system 36 evenly distributes the hot gas into the mass of fly ash in chamber 27 thereby heating the fly ash to a selected temperature. After a selected residence time at this temperature, at least a portion of the ammoniated compounds decompose into ammonia and other gases such as SO 2 .
  • the recovered ammonia along with the now cooler exhaust gas and any other gaseous by-products is output to the pipe 40(1) which is connected to pipe 40(2) and to pipe 40(3), although the ammonia could be output in other manners and configurations, such as to a storage container, hi this particular embodiment, the pipe 40(2) supplies a portion of the recovered ammonia stream to the ammonia injection system 22 and the pipe 40(3) supplies a portion of the recovered ammonia stream to the ammonia injection system 20.
  • the temperature of the hot exhaust emission gas will determine how much of the gas must be mixed with the fly ash to achieve the selected fly ash temperature.
  • the selected plan area of chamber 27 will determine the velocity of the hot exhaust emission gas through the fly ash. If this velocity is low, the fly ash may be considered a "fixed bed”. At higher velocities the fly ash will become “aerated” and at still higher velocities "fluidized” (at even higher velocities, the fly ash would be simply pneumatically transported out of chamber 27, but this is not a useful state). Either fixed bed, aerated or fluidized designs are workable, but require different types of equipment for the gas mixing system 36. As is apparent, these relationships are relatively simple and optimization of the design specifics may be accomplished by one of ordinary skill.
  • the mixed and heated fly ash particles are output from the chamber 27 to the collection bin 28.
  • the fly ash particles Prior to the ammonia recovery system 26, with the ammoniated compounds resulting from the additional ammonia injected to reduce the amount of sulfur trioxide, the fly ash particles have an ammonia content which may make them unsuitable for use in other applications.
  • the ammonia recovery system 26 at least a portion of the ammonia is recovered and removed from the fly ash particles so that the fly ash particles can still be used for other applications, such as a substitute for a portion of the cement in concrete.
  • the present invention provides an effective system and method for controlling and reducing sulfur trioxides in exhaust emission using ammonia at injection rates that prevent formation of undesirable sticky ammoniated compounds that could damage downstream equipment. Additionally, the present invention is able to recapture and reuse at least a portion of the injected ammonia used in reducing the sulfur trioxide in exhaust emission. Further, with the additional processing to remove the ammonia the fly ash particles are in a suitable condition for use in other applications, such as for replacement of a portion of the Portland cement in concrete.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chimneys And Flues (AREA)
  • Treating Waste Gases (AREA)

Abstract

L'invention concerne un procédé et un système de contrôle d'une ou plusieurs émissions, qui comprennent l'introduction d'ammoniac destiné à réagir avec au moins une partie des trioxydes de soufre d'une émission de combustion (32) et qui entraînent la formation d'au moins un ou plusieurs composés ammoniaqués. Au moins une partie des particules de cendre volante et les composés ammoniaqués présents dans les émissions d'échappement sont précipités (24). Au moins une partie de l'ammoniac est récupérée (26) des composés ammoniaqués précipités et la chaleur de l'émission de combustion (38(3)) et l'ammoniac récupéré (40(1)) sont réutilisés.
PCT/US2006/024835 2006-06-26 2006-06-26 systÈmes de contrÔle d'Émissions et LEURS procÉdÉs Ceased WO2008002290A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US2006/024835 WO2008002290A1 (fr) 2006-06-26 2006-06-26 systÈmes de contrÔle d'Émissions et LEURS procÉdÉs

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2006/024835 WO2008002290A1 (fr) 2006-06-26 2006-06-26 systÈmes de contrÔle d'Émissions et LEURS procÉdÉs

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4003986A (en) * 1973-03-14 1977-01-18 Lewis Jr George W Process for producing sulfur from sulfur dioxide or ammonium sulfites
US4064219A (en) * 1972-02-29 1977-12-20 Mitsubishi Jukogyo Kabushiki Kaisha Method of injecting ammonia into a flue for waste gases
US5051245A (en) * 1990-06-21 1991-09-24 Gas Desulfurization Corp. Ammonia for the desulfurization of sulfur containing gases
US6605263B2 (en) * 2001-12-06 2003-08-12 Powerspan Corp. Sulfur dioxide removal using ammonia
US6863875B1 (en) * 1998-04-13 2005-03-08 Mitsubishi Heavy Industries, Ltd. Flue gas treating system and process

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4064219A (en) * 1972-02-29 1977-12-20 Mitsubishi Jukogyo Kabushiki Kaisha Method of injecting ammonia into a flue for waste gases
US4003986A (en) * 1973-03-14 1977-01-18 Lewis Jr George W Process for producing sulfur from sulfur dioxide or ammonium sulfites
US5051245A (en) * 1990-06-21 1991-09-24 Gas Desulfurization Corp. Ammonia for the desulfurization of sulfur containing gases
US6863875B1 (en) * 1998-04-13 2005-03-08 Mitsubishi Heavy Industries, Ltd. Flue gas treating system and process
US6605263B2 (en) * 2001-12-06 2003-08-12 Powerspan Corp. Sulfur dioxide removal using ammonia

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