EP3043890A1 - Traitement des oxydes d'azote dans les flux de gaz de combustion - Google Patents

Traitement des oxydes d'azote dans les flux de gaz de combustion

Info

Publication number
EP3043890A1
EP3043890A1 EP14843945.8A EP14843945A EP3043890A1 EP 3043890 A1 EP3043890 A1 EP 3043890A1 EP 14843945 A EP14843945 A EP 14843945A EP 3043890 A1 EP3043890 A1 EP 3043890A1
Authority
EP
European Patent Office
Prior art keywords
gas stream
flue gas
urea
reagent
carbamide peroxide
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.)
Withdrawn
Application number
EP14843945.8A
Other languages
German (de)
English (en)
Other versions
EP3043890A4 (fr
Inventor
Philip A. Block
Timothy HOLTZ
Elena Pisanova
John M. ROVISON Jr.
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.)
Evonik Active Oxygens LLC
Original Assignee
Peroxychem LLC
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 Peroxychem LLC filed Critical Peroxychem LLC
Priority claimed from PCT/US2014/055630 external-priority patent/WO2015039019A1/fr
Publication of EP3043890A1 publication Critical patent/EP3043890A1/fr
Publication of EP3043890A4 publication Critical patent/EP3043890A4/fr
Withdrawn legal-status Critical Current

Links

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
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B01D53/565—Nitrogen oxides by treating the gases with solids
    • 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
    • B01D53/77—Liquid phase processes
    • B01D53/79—Injecting reactants
    • 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
    • B01D53/81—Solid phase processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/106—Peroxides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide

Definitions

  • the present invention relates to the treatment of a combustion flue gas stream from a stationary source to remove nitrogen oxide (NO) before the gas stream is released into the atmosphere.
  • NO nitrogen oxide
  • the primary air pollutants formed by these stationary high temperature combustion sources are sulfur oxides (e.g. , S0 2 and SO 3 ), also called SOx gases, and nitrogen oxides, also called ⁇ gases, both of which are acid gases.
  • SOx gases sulfur oxides
  • ⁇ gases nitrogen oxides
  • Other combustion pollutants of concern in these combustion flue gases include other acid gases such as HC1 and HF, Hg (mercury), C(3 ⁇ 4 and particulates.
  • SCR Selective Non-Catalytic Reduction
  • SNCR Selective Non-Catalytic Reduction
  • the Selective Catalytic Reduction procedure utilizes a catalytic bed or system to treat a flue gas stream for the selective conversion (reduction) of ⁇ to N 2 .
  • the SCR procedure normally utilizes ammonia or urea as a reactant that is injected into the flue gas stream upstream, prior to their being contacted with the catalyst, SCR systems in commercial use typically achieve ⁇ removal rates of 80-90%, but improved catalyst systems reportedly provide over 90% removal rates.
  • the Selective Non-catalytic Reduction procedure is analogous to SCR except that no catalyst is employed in the treatment of a flue gas stream with ammoni or urea for the selective reduction of ⁇ to N 2 .
  • High treatment temperatures are required for the reduction reaction in SNCR, in the absence of the catalysts used in SCR systems.
  • SNCR systems are favored for retrofit of smaller electric power utility plants because of their simplified installation and modest equipment requirements.
  • Drawbacks to commercial SNCR. systems are their requirement of very high and narrow temperature ranges to effect conversion of ⁇ to N, which often results in undesirable reaction byproducts, and their ⁇ removal rates of only 30-70% .
  • the present invention provides an air pollution retrofit system that is particularly well suited to (but not limited to) improving the performance of removing ⁇ in SNCR- treaied combustion flue gas streams, utilizing a ⁇ reduction reagent.
  • the novel ⁇ treatment system of this invention is not taught in prior art treatments for abating SOx and ⁇ contaminants in combustion flue gas streams.
  • U.S. Patent No. 4,213,944 of Azuhata et at. discloses a process for removing nitrogen oxides from a hot gas stream containing the same by adding a reducing agent, preferably ammonia, and hydrogen peroxide into hot gas stream at a temperature of 400-1200°C to decompose the nitrogen oxides to nitrogen gas and water.
  • the hydrogen peroxide is added concurrently with the ammonia and is said to increase the activity of the ammonia, particularly at gas temperatures of 400-8G0°C, by decomposing the ammonia to make it reactive with the ⁇ .
  • Sufficient hydrogen peroxide is added with the ammonia so that excess unreacted ammonia is also decomposed,
  • a ⁇ treatment technique analogous to that described in the Azuhata. patent involves treatment of a combustion flue gas containing ⁇ with ammonia and hydrogen peroxide and is described by D.A. Cooper in "The Influence of Ammonia and Hydrogen Peroxide Addition on NOx Emissions in the Flue Gas Channel of a 16 MW Coal-fired Fluidised Bed Combustor," Journal of the Institute of Energy, vol. 61, no. 447 (1988), pp. 78- 84.
  • U.S. Patents No. 5, 120,508, and 4,783,325 of Jones disclose methods of converting NO to NO ? , in a flue gas stream by injecting a gas containing a peroxyl initiator and oxygen into the NO-containing gas stream.
  • the peroxyl initiator is preferably propane but may also be other hydrocarbons or hydrogen peroxide or hydrogen.
  • the resultant NO ? - containing gas stream is then treated in an absorption section to remove ⁇ and SOx with a dry sorbent such as nahcolite or trona, the dry sorbent being captured in a baghouse before the treated gas stream is discharged to the atmosphere.
  • Zamansky et al. discloses a method for removing NO, SO 3 , CO, light hydrocarbons and mercury vapor (Tig) from combustion flue gas by injecting into the gas stream atomized droplets of either hydrogen peroxide or a mixture of hydrogen peroxide and methanol, to convert the respective gas contaminants to NO?, SO ? ., CO ? , (for the CO and light hydrocarbons) and HgO.
  • the treatment is carried out at a gas temperature of about 377°C to about 827°C, and the reaction products are subsequently removed in a downstream scrubbing operation.
  • the treatment also may be carried out in combination with SNCR ⁇ reduction technology, with the 8NCR- treated combustion gas stream being treated downstream with the H 2 0 2 or IT2O2/CIT OH injection treatment.
  • the method is also described by Zamansky et al. in Preprints of Papers, American Chemical Society (ACS), Div. of Fuel Chemistry; Journal Vol. 40; Issue No. 4; Conference 210, Natl. Meeting of the ACS, Chicago, IL, 20-25 Aug. 1995, pp. 1039-1044.
  • U.S. Patent No. 6,676,912 of Cooper et al. discloses a method of removing NO from stationary combustion gas streams by injection of H 2 0 2 into the gas stream to oxidize NO to NO? and HNO 3 and HNQ ? , which species are more readily recovered via aqueous wet scrubbing.
  • the nitrogen acids and residual NO ? are then removed via wet scrubbing with water or an aqueous alkaline medium or via passage of the flue gas stream through a particulate alkaline sorbent in a baghouse.
  • the method may optionally include a preliminary flue gas desulfurization scrubbing step to remove SO?, prior to the H ? Q? injection.
  • U.S. Patent No. 6,676,912 of Cooper et al. is hereby incorporated by reference for its disclosures about the reaction of H 2 0 2 and ⁇ and related reactions.
  • U.S. Patent No. 8, 147,785 of Pfeffer et al. describes a method for removing residual unreacted ammonia (ammonia slip) that is present in a combustion flue gas stream that has been treated via SCR or SNCR ⁇ treatment systems using ammonia or urea.
  • the flue gas stream is treated downstream of the SCR or SNCR operation with aqueous hydrogen peroxide to remove residual unreacted ammonia.
  • the present invention provides a method for the removal of ⁇ in a SNCR system that enables the removal of ⁇ from the gas stream at reduced operating temperatures and that does not require use of ammonia as reducing agent.
  • nitrogen oxides are removed from a flue gas stream in a method comprising introducing a reagent or a mixture comprising carbamide peroxide and water into a stationary-source ⁇ -containing combustion flue gas stream at a temperature between about 300°C to about 800°C.
  • the reagent or the mixture is in an amount sufficient to react with nitrogen oxides ( ⁇ ) such as NO in the flue gas stream, to yield a flue gas stream having a reduced concentration of nitrogen oxides ( ⁇ ) such as NO.
  • Figure 1 is a graph that shows the results of the study described in Comparative Example 4, in which hydrogen peroxide alone was used to treat a gas stream containing NO.
  • Figure 1 shows concentrations of NO, NO2 and NO + NO2 ( ⁇ ) in the H202-treated gas stream as a function of time during the study.
  • Figure 2 is a graph that shows the results of the study described in Example 5, in which carbamide peroxide aqueous solution was used to treat a gas stream containing NO.
  • Figure 2 shows concentrations of NO, NO 2 and NO + NO 2 ( ⁇ ) in the carbamide peroxide treated gas stream as a function of time during the study.
  • Figures 3-7 are graphs that shows the results of the study described in Examples 6 and 7, in which carbamide peroxide (Figs. 5 and 7) and urea alone (Figs. 3, 4, and 6), were used to treat gas streams containing NO.
  • the Figures show concentrations of NO, NO 2 and NO + NO 2 ( ⁇ ) in the reagent-treated gas streams as a function of time during the studies.
  • Figure 8 is a schematic flow diagram illustrating a preferred embodiment of the combustion flue gas ⁇ treatment process of this invention that is described in Example 10.
  • the present invention is a treatment method for removing nitrogen oxides ( ⁇ ) from a combustion flue gas stream from a stationary combustion source, e.g., an electric power plant generating facility, by conversion of the nitrogen oxides, particularly NO, to water and nitrogen gas using a two component reagent that serves as the reducing agent.
  • the invention is particularly useful for effecting the conversion (reduction) of nitrogen oxides at relatively low temperatures, without the need for a catalyst such as is typically used in SCR operations to effect reduction of ⁇ .
  • the ⁇ treatment method of this invention accomplishes this objective using a reagent that is urea in combination with hydrogen peroxide such as carbamide peroxide, in the absence of a catalyst, such as the catalysts typically utilized in SCR operations.
  • Carbamide peroxide [(NH ⁇ CO ⁇ 3 ⁇ 4(3 ⁇ 4] is a solid adduct of 1 mole of Hydrogen peroxide with 1 mole of urea.
  • the reagent comprising carbamide peroxide and water is injected or otherwise introduced into a flue gas containing ⁇ such as NO to effect removal (conversion) of a substantial portion of the ⁇ in the treated gas stream, as is described in more detail below.
  • the reagent can comprises a mixture (such as a solution or a slurry) of carbamide peroxide and water prepared before introduced into a flue gas containing ⁇ .
  • the mixture can further comprise additional urea or hydrogen peroxide.
  • the carbamide peroxide and the water can be also introduced separately and concurrently into the flue gas stream, as a first stream containing solid carbamide peroxide and a second stream containing water.
  • the invention is particularly useful for modifying the operation of conventional Selective Non-Catalytic Reduction reactor systems to be adapted to operation at reduced temperature ranges, e.g., below 800°C, using the urea-based reagent of this invention instead of ammonia as the reducing agent.
  • the combustion flue gas stream exiting the combustion zone of a stationary source contains a variety of components that, are desirably reduced or removed from the flue gas prior to its being discharged to the atmosphere, among which are the ' ⁇ components treated according to the present invention.
  • the precise composition of the combustion flue gas depends primarily on the nature of the fuel and on the furnace design and operating parameters.
  • the fuel may be, e.g., coal, oil, coke or natural gas, etc., and in the case of coal, coal may be high sulfur or low sulfur, bituminous or anthracite, etc.
  • a representative flue gas stream obtained from combustion of high sulfur coal containing 2.5 w % sulfur, burned using 10% excess air has the composition shown in Table 1.
  • the NO concentration in the flue gas stream is typical of that expected from the burning of high sulfur coal in a furnace that is not equipped with low ⁇ burners.
  • the NO ? , concentration typically represents about 5% of the total ⁇ .
  • the S0 2 concentration in the flue gas stream is relatively high, as would be expected from the burning of high sulfur coal.
  • the SO 3 concentration is typically only about 1% of the SO? concentration.
  • the foregoing flue gas composition is simply meant to be illustrative of a typical combustion flue gas stream.
  • the present invention is adapted to be used with a wide range of different flue gas compositions from a variety of stationary sources and air pollution control systems, within the parameters described in more detail below for the method of this invention.
  • the ⁇ treatment method of the present invention involves use of carbamide peroxide, in combination with water, as the reagent to effect reduction of ⁇ compounds present in the flue gas stream being treated.
  • the reagents, carbamide peroxide and water are injected or otherwise introduced into the flue gas stream, preferably in aqueous form, e.g., as an aqueous solution or an aqueous slurry.
  • the reagent components are preferably combined prior to their injection or introduction into the flue gas stream.
  • the carbamide peroxide and water components may be introduced separately but concurrently into the flue gas stream being treated provided that good mixing of the two reagent components is ensured.
  • the carbamide peroxide component can be used in dry powder form when introduced into the flue gas stream.
  • aqueous reagent solution should be understood as meaning that the reagent components that are normally solids (urea or carbamide peroxide) are totally solubilized in the aqueous solution.
  • aqueous reagent slurry should be understood as meaning that the reagent components that are normally solids (urea or carbamide peroxide) may only be partially solubilized and that a portion of such solids are suspended as solids (preferably as finely- divided particulates) in the aqueous slurry.
  • aqueous reagent medium and aqueous medium should be understood to include or encompass both solutions and slurries.
  • Carbamide peroxide is a solid adduet, which contains both urea and hydrogen peroxide, present in a 1 : 1 molar ratio.
  • Carbamide peroxide is preferably injected or introduced into the flue gas stream in aqueous form, e.g., as an aqueous solution.
  • the solubility of carbamide peroxide in water is relatively high, e.g., about 50 g. carbamide peroxide /100 ml. water at 20°C.
  • carbamide peroxide may be introduced as a solid into the flue gas stream, e.g., as a finely-divided particulate solid or powder, or as a concentrated aqueous slurry containing carbamide peroxide that is only partially solubilized in the aqueous medium.
  • the particulate solid (carbamide peroxide in an aqueous medium or carbamide peroxide injected as a solid) should have a relatively small particle size in order to maximize the surface-to-volume ratio, a factor that can enhance the effectiveness of the gas-solid interaction between the ⁇ and solid and between the hydrogen peroxide and solid.
  • the mean particle size of the particulate solid is preferably be less than about 100 ⁇ , more preferably less than about 70 ⁇ , and most preferably less than about 40 ⁇ .
  • the second important component of the reagent composition is water. It is known that water participates in the radical reaction initiated by hydrogen peroxide and thus is important for NOx reduction. Tims, the water functions as an active component in the reaction and not simply a carrier or a solute
  • the concentration of water can vary, but the molar ratio of water to carbamide peroxide in the aqueous solution is preferably maintained within a range of from about 5: 1 to about 500: 1, and more preferably within a range of from about 50: 1 to about 200: 1 H2O : carbamide peroxide.
  • the aqueous reagent solution preferably contains at least 1 wt. % total of the carbamide peroxide, more preferably at least about 3 wt. % total of t carbamide peroxide, and most preferably at least about 5 wt. % carbamide peroxide.
  • Higher total concentrations of the carbamide peroxide in the aqueous reagent solution are feasible, e.g., 10 wt. % or more or even 20 wt. % or more of carbamide peroxide, with the recognition that very high total concentrations (e.g., above 50 wt. %) may exceed the maximum solubility of the carbamide peroxide, resulting in the formation of an aqueous slurry.
  • the molar ratio of urea to hydrogen peroxide in carbamide peroxide is 1 : 1.
  • solid urea or liquid aqueous solution of I i >() ⁇ can be added to the aqueous solution of carbamide peroxide.
  • the reagent used in this invention can comprise a mixture of carbamide peroxide, water, and urea.
  • the molar ratio of the carbamide peroxide to the urea to the water can be in the range of from about 0.25: 1 :50 to about 20: 1 : 1000.
  • the reagent used can comprise a mixture of carbamide peroxide, water, and H 2 0 2 .
  • the molar ratio of the carbamide peroxide to the H 2 0 2 to the water can be in the range of from about 0.5: 1 :50 to about 10: 1 :500.
  • Urea H 2 CONH 2
  • Urea is a. stable solid at room temperature.
  • Urea is water soluble and may be completely dissolved in water or in aqueous solutions also containing carbamide peroxide, for subsequent injection into a flue gas stream being treated in the method of this invention.
  • the concentration range of such urea - hydrogen peroxide solutions may vary over a relatively wide range, given that the maximum solubility of urea (or carbamide peroxide) in aqueous media is relatively high.
  • the molar ratio of carbamide peroxide to urea in the aqueous solution is preferably maintained within a range of from about 0.25: 1 to about 20: 1 carbamide peroxide to urea.
  • the hydrogen peroxide is preferably utilized as aqueous hydrogen peroxide. It can be added to an aqueous solution of carbamide peroxide, in various proportions, which allows to change the urea to H 2 O 2 ratio in the reagent used for NOx reduction.
  • the molar ratio of carbamide peroxide to H 2 O 2 in the aqueous solution is preferably maintained within a range of from about 0.5: 1 to about 10: 1 carbamide peroxide to H 2 O 2 .
  • the molar ratio of urea to hydrogen peroxide in the aqueous solution is preferably maintained within a range of from about 0.1 : 1 urea:H202 (i.e., 10: 1 H 2 0 2 :urea) to about 5: 1 urea:H 2 0 2 (i.e., 1 :5 H ⁇ C ⁇ urea), and more preferably within a range of from about 0.2: 1 urea:H 2 0 2 (i.e., 5: 1 H 2 0 2 :urea) to about 3: 1 urea:H 2 0 2 .
  • the molar ratio of urea to hydrogen peroxide is preferably at least equimolar, 1 : 1 urea: H 2 O 2 . More preferably, the molar ratio of urea to hydrogen peroxide provides a molar excess of urea relative to the hydrogen peroxide. More preferably the amount of urea present in the aqueous solution provides a molar excess of urea with respect to the hydrogen peroxide, e.g. , at least about 1.1 moles urea per 1 mole H 2 O 2 , up to about 3 moles urea per 1 mole H 2 O 2 and, more preferably, up to about 2: 1 :urea: H 2 0 2 .
  • Carbamide peroxide and urea solutions typically have a relatively neutral pH.
  • Aqueous solutions containing both urea and hydrogen peroxide are slightly acidic, e.g., about pH 3.5 to about pH 5.5, which promotes stability of the hydrogen peroxide against decomposition.
  • Ammonia (the preferred reducing agent in conventional SCR and SNCR ⁇ treatment operations), by contrast, lacks many of the advantages associated with urea just mentioned. Ammonia is a corrosive gas and in aqueous solution has a relatively alkaline pH, 1 1-12.
  • aqueous solutions that contain both ammonia and hydrogen peroxide are typically unstable, with the hydrogen peroxide being susceptible to decomposition at room temperature due to the alkaline solution pH.
  • Ammonia also has a tendency to react with SO 3 in SOx- and ⁇ -containing flue gas streams, leading to formation of ammonium sulfate, a corrosive and sticky solid salt that can lead to plugging in flue gas stream ductwork.
  • the concentration of hydrogen peroxide in the aqueous reagent solution may vary over a wide concentration range, from about 0.5 wi. % to about 50 wi % H 2 0 2 .
  • the preferred concentration range for the hydrogen peroxide component in the aqueous reagent solution is desirably in the range of from about 1 wi % to about 40 wi % H 2 0 2 , preferably in the range of from about 2 w % to about 30 wi % H 2 0 3 ⁇ 4 and more preferably in the range of from about 3 wi % to about 20 wi. % i I ;( ' ) >.
  • the hydrogen peroxide component in the aqueous reagent solution is present at a concentration of at least 5 wi % H 2 0 2 .
  • the preferred concentration range for the hydrogen peroxide component in the aqueous reagent solution is normally determined indirectly, by the choice of (1) of the urea concentration desired in the aqueous medium (a decision that normally takes into
  • the source aqueous hydrogen peroxide used in the present invention may have a wide range of aqueous solution concentrations, with aqueous solutions preferably containing about 10 wt. % to about 50 wt. % H 2 0 2 and those containing from about 20 wt. % to about 40 wt. % H 2 0 2 being more preferred. Aqueous hydrogen peroxide solutions within these concentration ranges are readily available from commercial suppliers, as stabilized H 2 0 2 solutions.
  • Concentrations of aqueous H 2 0 2 above 50 wt. % H 2 0 2 are feasible but require stringent handling and safety measures and are best avoided for that reason.
  • Concentrations of aqueous H 2 0 2 below 10 wt. % H 2 0 2 are likewise feasible but are relatively dilute, requiring relatively larger volumes to provide the same amount of 3 ⁇ 40 2 as provided in much smaller volumes of more concentrated aqueous solutions.
  • the activity of the hydrogen peroxide as a reagent in combination with the urea reagent component may optionally be enhanced or increased, in the present invention, by the use of one or more activators in conjunction with the aqueous hydrogen peroxide.
  • the activator may be added or otherwise introduced into the aqueous solution containing urea and hydrogen peroxide shortly before that aqueous solution is injected into the ⁇ -containing flue gas stream or may be introduced concurrently with the aqueous reagent solution during the injection procedure, provided that there is good mixing between the two.
  • the activator may alternatively be added to the source aqueous hydrogen peroxide thai is used to prepare the aqueous solution containing urea and hydrogen peroxide
  • Activators for hydrogen peroxide include metal ions (e.g.,. iron, copper, manganese, chromium, nickel), metals (e.g., platinum, silver) and metal compounds (e.g., oxides, hydroxides or sulfides, e.g., of manganese, iron, copper, palladium).
  • metal ions e.g.,. iron, copper, manganese, chromium, nickel
  • metals e.g., platinum, silver
  • metal compounds e.g., oxides, hydroxides or sulfides, e.g., of manganese, iron, copper, palladium.
  • a preferred activator is iron and, as is evident for the exemplified metals, transition metals, including the heavy metal s, are also preferred.
  • Combinations of metal activators may be used, with iron and copper being a preferred synergistic combination.
  • hydrogen peroxide activators include oxidizing agents such as ozone, hypochlorite (e.g., sodium or calcium hypochlorite), chlorite (e.g., sodium chlorite), chlorate (e.g., sodium, potassium, or magnesium chlorate), and the like.
  • oxidizing agents such as ozone, hypochlorite (e.g., sodium or calcium hypochlorite), chlorite (e.g., sodium chlorite), chlorate (e.g., sodium, potassium, or magnesium chlorate), and the like.
  • the hydrogen peroxide activator may be introduced into the aqueous medium containing urea and hydrogen peroxide (or into the source aqueous hydrogen peroxide) in dissolved form or in suspended form. Small amounts of activator, in the range of parts per million, are normally sufficient to enhance the hydrogen peroxide activity.
  • a noteworthy and surprising aspect of the present invention is that hydrogen peroxide, when used in combination with the urea in the two component reagent employed in this invention, appears not to function as an oxidizer with respect to the ⁇ components in the flue gas stream being treated. Hydrogen peroxide, a strong oxidizer, will result in oxidation of NO to N(1 ⁇ 4 i a flue gas stream containing ⁇ , if introduced into the gas stream as the sole reagent; see Comparative Example 4, below,
  • Hydrogen peroxide when used in combination with urea, in the reagent employed in the method of this invention, appears to function as an activator or agent that enhances the reducing functionality of the urea (with respect to the ⁇ in the flue gas stream being treated), rather than oxidizing NO present in the gas stream.
  • the hydrogen peroxide in this unique role enables the urea to provide its desired reducing functionality at much lower flue gas stream temperatures than are conventionally used with urea alone.
  • the aqueous reagent medium containing urea and hydrogen peroxide that is employed as the reducing agent in the method of this invention for reaction with ⁇ in flue gas streams may be used over a wide range of concentrations, with respect to the total amount of urea and hydrogen peroxide present in the aqueous solution or medium.
  • the 1 : 1 molar ratio of urea: H2O2 provided by carbamide peroxide may be adjusted above or below this equimolar amount via supplemental addition of urea or hydrogen peroxide.
  • the aqueous reagent solution is preferably within a temperature of about 10°C to about 50°C, more preferably about 15°C to about 30°C, prior to its injection or introduction into the flue gas stream. H igher or lower temperatures outside of the preferred range are also feasible, but very low solution temperatures may limit the maximum solubility of urea and very high solution temperatures may result in unwanted decomposition of the hydrogen peroxide, prior to injection of the solution.
  • This reduction reaction converts NO to N 2 and results in formation of nitrogen (N 2 ), carbon dioxide (C0 2 ) and water (H 2 0), all gaseous reaction products.
  • N 2 nitrogen
  • C0 2 carbon dioxide
  • H 2 0 water
  • reaction products are gaseous compounds that are typically present in a flue gas stream from a stationary-source combustion source and thus do not introduce any new species or unwanted reaction byproducts into the treated gas stream.
  • the urea and hydrogen peroxide reagent employed in this invention may be considered environmentally friendly.
  • the amount of reagent introduced into the flue gas stream for reaction with the ⁇ present in the gas stream is normally controlled via the flow rate of reagent introduced into the gas stream, to provide the desired amount of urea or hydrogen peroxide relative to the NO to be reacted.
  • the amount of reagent introduced into the gas stream should provide a minimal concentration of both urea and H 2 0 2 in the gas stream of at least 100 ppm, and minimal concentration of water vapor in the gas stream should be at least 1000 ppm.
  • the amount (flow rate) of reagent introduced into the flue gas stream is preferably adjusted to provide a molar ratio of urea: NO (i.e., urea in the reagent : NO in the gas stream) within the range of from about 0.1 : 1 urea: NO to about 10: 1 urea: NO and more preferably within the range of from about 0.2: 1 urea: NO to about 5: 1 urea: NO and most preferably within the range of from about 0.5: 1 urea: NO to about 3 : 1 urea: NO.
  • NO i.e., urea in the reagent : NO in the gas stream
  • the molar ratio of urea to NO is preferably slightly less than or greater than stoichiometric (i.e., +/- 20% of stoichiometric, which is about 2: 1 urea:NO - see reaction (1) above), so as to minimize the formation of unwanted reaction byproducts, e.g., ammonia (NH 3 ) in the treated flue gas stream. More preferably, the reagent is introduced into the flue gas stream in an amount that provides at least a stoichiometric molar amount of urea for reaction with the NO in the flue gas stream being treated.
  • the urea - hydrogen peroxide treatment method of this invention is primarily directed to removal of ⁇ in the treated flue gas stream and, as noted above, an excess of hydrogen peroxide (with respect to the urea reagent component) may be employed in the present invention. Any unreacted hydrogen peroxide excess that remains after reaction of the urea with ⁇ is also available to react with other contaminants in the flue gas stream, e.g., SOx, particularly SO 3 , converting them to less objectionable or more readily removed species.
  • the aqueous solution containing urea and hydrogen peroxide that is employed as the reagent in the method of this range typically has a solution pH that is slightly acidic, e.g., in the range of about pH 3.5 to about pH 5.5.
  • the slightly acidic pH values of aqueous solutions containing urea and hydrogen peroxide is beneficial for promoting stability of the hydrogen peroxide in solution against decomposition.
  • aqueous ammonia solutions are alkaline, having pH values in the range of about pH 11-12.
  • the pH of solutions containing both ammonia and hydrogen peroxide are likewise alkaline, typically in the range of about pH 10-1 1, and such alkaline pH ranges (unlike acidic pH values) are detrimental to the stability of hydrogen peroxide.
  • the aqueous solution (or aqueous medium) containing urea and hydrogen peroxide may be injected into the ⁇ -containing flue gas stream using conventional injection equipment normally used for introducing an aqueous solution or aqueous slurry into a gas stream.
  • the aqueous solution is preferably injected, i.e., introduced, into the flue gas stream as fine liquid streams or, preferably, as a. spray, such as atomized droplets, through one or more spray nozzles.
  • the spray nozzles or other introduction means e.g., perforated pipe
  • the injection system design should include provisions for ensuring that the hydrogen peroxide contained in the aqueous solution does not become prematurely heated or overheated (and vulnerable to decomposition) prior to its introduction into the hot flue gas stream.
  • the reagent components, urea and hydrogen peroxide are injected or otherwise introduced into the flue gas stream concurrently and preferably in combination with each other.
  • the reagent is preferably in aqueous form, e.g., preferably as an aqueous solution containing urea and hydrogen peroxide.
  • the urea and hydrogen peroxide reagent components are preferably combined prior to their injection or introduction into the flue gas stream, but, alternatively, the urea and hydrogen peroxide components may be introduced separately but concurrently into the flue gas stream being treated provided that good mixing of the two reagent components is ensured.
  • Separate aqueous streams containing, respectively, urea and hydrogen peroxide may be introduced concurrently into the flue gas stream being treated, with mixing of the two components being effected in the flue gas stream.
  • Such concurrent introduction of the two component streams may be accomplished using separate nozzle systems for each component or by using individual nozzles that have separate internal channels for spraying the two liquid streams concurrently as atomized droplets of each which become intermixed in the flue gas stream.
  • This procedure of introducing the two component streams concurrently has the advantage of permitting quick and easy adjustment of the molar ratio of urea:H 2 0 2 , as may be needed, to compensate for changes in the flue gas composition or other gas stream characteristics.
  • the reagent may also be introduced into the flue gas stream being treated in solid form, e.g. , powdered or particulate carbamide peroxide or urea, or as an aqueous medium that also contains solids, e.g., as an aqueous slurry containing urea and hydrogen peroxide (the slurry containing urea solids, dissolved urea and aqueous hydrogen peroxide.)
  • carbamide peroxide or urea components of the reagent may be introduced as a powdered solid or as an aqueous slurry (in particulate and partially solubilized form), they are preferably introduced into the flue gas stream being treated as an aqueous solution (completely solubilized) and more preferably is in an aqueous solution containing urea and hydrogen peroxide.
  • the hydrogen peroxide is preferably utilized as an aqueous hydrogen peroxide solution and is normally introduced into the flue gas stream as such, preferably in
  • the ⁇ treatment method of this invention using the urea-hydrogen peroxide reagent is normally carried out with flue gas stream temperatures ranging from about 300°C to about 800°C, without need for a catalyst such as is used in conventional SCR. ⁇ operations that utilize a catalyst in order to operate at temperatures below 800°C. Flue gas stream temperatures are preferably within the range of from about 350°C to about 750°C, more preferably within the range of from about 350°C to about 650 C C, still more preferably within the range of about from 350°C to about 600°C, and most preferably within the range of from about 400°C to about 550°C for urea-hydrogen peroxide treatment method of this invention.
  • urea-hydrogen peroxide injection in the present invention, may be carried out by locating the injection point in the combustion gas stream at a suitable point where the gas stream temperature is within the desired temperature range, e.g., upstream of an economizer and downstream from the combustion unit in the flue gas stream ducting from an electric utility power plant.
  • the method of the present invention may be carried out with existing SNCR-ireated flue gas streams, which are typically operated at temperatures well in excess of 800°C. Since the inventive method allows operation at lower temperature ranges than the veiy high temperatures conventionally used with SNCR treatments, the flue gas stream may optionally be subjected to a heat exchange step upstream of the SNCR operation to recover heat values from the flue gas stream and thus effect a lowering of the flue gas stream temperature to the preferred operating temperatures ranges employed in this invention, e.g. s within a temperature range of from about 300°C to about 800°C.
  • Residence time required for reaction of the urea -hydrogen peroxide reagent and ⁇ , e.g., NO, after injection or introduction of the reagent into the flue gas stream is typically very short, from a fraction of a second, e.g., 0.01 second, to less than a few seconds, e.g., up to about 5 seconds.
  • Preferred residence times for the injected reagent being in contact with the ⁇ -containing gas stream are generally less than about 2 seconds.
  • the optimum residence time will normally depend on factors such as the temperature of the flue gas stream, with higher gas temperatures generally providing more rapid reaction.
  • the urea and hydrogen peroxide reagent employed in the method of the present invention is normally capable of reducing the initial NO concentration in the flue gas stream to significantly lower NO concentrations in treated flue gas stream, such that the treated gas stream has a reduced concentration of NO.
  • Sufficient urea and hydrogen peroxide reagent is desirably employed in the method of this invention to reduce the NO concentration in the flue gas stream to less than about 60% of its initial concentration, prior to treatment according to this invention.
  • the urea and hydrogen peroxide reagent treatment is sufficient to reduce the NO present in the treated flue gas stream to less than about 50%, and more preferably less than about 40%, of its initial concentration in the flue gas stream prior to treatment.
  • the urea and hydrogen peroxide reagent employed in the method of the present invention is preferably utilized in a selective non-catalytic reduction operation to achieve these removal efficiencies.
  • the present invention for reducing ⁇ in ⁇ -containing flue gas streams may also be employed in conjunction with desulfurization operations, for reducing the
  • Such optional desulfurization unit operations may be carried out either upstream or downstream of the ⁇ treatment method of the present.
  • the desulfurization is carried out on the ⁇ -depleted flue gas stream at a location downstream of the urea- hydrogen peroxide treatment method of the present invention. This is particularly so in the case of wet desulfurization operations being employed, since exiting flue gas stream temperatures are significantly reduced upon passage through wet scrubbers or absorbers.
  • the SOx in combustion flue gas streams is primarily sulfur dioxide (S0 2 ) and sulfur trioxide (SO 3 ). These SOx components are normally formed during the combustion of sulfur- containing (sour) fuels, such as coal, coke or oil, and the flue gas streams that result from burning such sulfur-containing fuels, whether low-sulfur or high sulfur, consequently contain SOx contaminants.
  • sulfur- containing (sour) fuels such as coal, coke or oil
  • Sulfur dioxide is the predominant SOx component in flue gas streams, with sulfur trioxide, SO 3 , being produced in much smaller quantities than SO ? ..
  • Concentrations of SO? in flue gas streams from coal fired boilers are typically substantial, e.g., about 0.01 vol. % to about 0.5 vol. % S0 2 , with about 0.05 vol. % to about 0.3 vol. % S0 2 being typical.
  • Typical concentrations of S(3 ⁇ 4 in flue gas streams from coal fired boilers are about 10 ppni to about 30 ppm (by volume) SO 3 .
  • Conventional pollution control operations to remove ⁇ components from a flue gas stream e.g., via selective catalytic reduction (SCR), often result in an unwanted increased concentration of SO 3 , formed by the catalytic oxidation of S0 2 in the flue gas stream during SCR treatment, to levels that can double those normally present, e.g., to about 20 to about 60 ppm or more SO 3 .
  • the presence of catalytic metals, e.g. , vanadium or nickel, in some fuels can also result in the generation of additional sulfur trioxide.
  • SOx contaminants are desirably removed, or their concentrations reduced, in the combustion flue gas stream via desulfunzation procedures, prior to the flue gas stream being released into the atmosphere.
  • desuifurization operations are readily incorporated into an integrated air pollution control system that utilizes the present invention for ⁇ removal, in the treatment of a ⁇ - and SOx-containing combustion flue gas stream.
  • Desuifurization processes for removing SO? and/or SO 3 are well known in the air pollution control field.
  • Gas-liquid contactors or absorbers are widely used to remove SO 2 from waste flue gas streams, using an alkaline reagent- containing aqueous medium, e.g., in wet scaibbing systems utilizing lime, limestone or soda ash ( sodium carbonate).
  • concentrations employ alkali reagents in wet scrubbing, slurry injection or dry sorbent injection procedures. Some prior art desuifurization procedures are effective for removing both S0 2 and S0 3 .
  • the present invention may be adapted for use with many conventional
  • desuifurization systems whether employed to remove SOx components generally or SO? or SO 3 specifically.
  • desuifurization systems are preferably located downstream, for desuifurization of the ⁇ -depleted flue gas stream resulting from treatment according to the present invention.
  • Wet desuifurization systems are preferred for use in conjunction with the present invention, particularly wet scrubbing desui urization systems that employ lime, limestone or soda ash.
  • Upstream desulfurization may be desirable in situations where flue gas streams contain high concentrations of SO 3 . Injection of a dry soda-type sorbent or slurried soda-type sorbent can be used to remove a. significant portion of SO 3 upstream of the urea - hydrogen peroxide treatment of a ⁇ - and SOx-containing flue gas stream according to the present invention,
  • Examples 1-3 utilized the following laboratory apparatus.
  • the lab set-up included a pre-heater consisting of a quartz tube heated by a Lindberg tube furnace; an insulated heated tube reactor (diameter: 10 mm, length: 1,200 mm); and auxiliary equipment including a syringe pump, temperature controllers, gas flow meters, gas distribution panel, cold trap, and mist catcher.
  • a gas mixture consisting of NO, ()?, and N 2 was introduced as a gas stream first into the pre-heater and then into the insulated heated tube reactor heated to a predetermined temperature.
  • the gas components of the gas mixture were sourced from nitrogen gas, air, and NO in nitrogen (390 ppm NO in N 2 ). Concentrations of each component in the gas mixture were adjusted by a flow rate meter.
  • An injection inlet was provided at a position at the entrance to (upstream of) the insulated heated tube reactor, and aqueous urea-33 ⁇ 4Q 2 reagent solutions were injected into the flowing gas stream through a stainless steel tube with a diameter of 1.0 mm.
  • Example 1 studied the effect of using varying amounts of carbamide peroxide reagent relative to the amount of NO in the gas stream. Five different molar ratios of reagent to NO in the inlet gas stream were used to study the reagent concentration effect (relative to the NO) on the removal of NO from the gas stream.
  • Example 1 the aqueous solution of the reagent was prepared by dissolution of carbamide peroxide, a solid adduct of urea and hydrogen peroxide, in water to prepare an aqueous solution that contained 5.0 wt. % carbamide peroxide, i.e., corresponding to 3.2 wt. % urea and 1.8 wt. % H 2 0 2 .
  • Temperature of the gas stream in the tube reactor was 465°C.
  • the gas stream flow rate was 3.2 L/min.
  • Table 2 summarizes the results for the five operating runs, with the tube reactor inlet and outlet NO concentrations being shown along with the percentage NO reduction achieved.
  • Example 2 studied the effect of using three different urea-to-hydrogen peroxide molar ratios on the removal of NO from a gas stream.
  • the apparatus used for Exampl e 2 was the same as that utilized in Example 1.
  • Example 2 the urea (in solid form) or hydrogen peroxide (50% 3 ⁇ 40 2 source solution) was combined with carbamide peroxide and water to prepare aqueous solutions containing urea and hydrogen peroxide in three different molar ratios: 1.5 : 1, 1 : 1 and 0.67: 1 urea:!3 ⁇ 402 in the aqueous reagent solutions.
  • Example 1 (corresponding to 3.2 wt. % urea and 1.8 wt. % H2O2) as were used in Example 1.
  • Example 1 The temperature of the gas stream in the tube reactor was 405°C, somewhat less than the 465°C used in Example 1.
  • the gas stream flow rate was 3.2 L/min., the same as used in Example 1.
  • Table 3 summarizes the three operating runs, with the tube reactor inlet and outlet NO concentrations being shown along with the percentage NO reduction achieved.
  • Example 3 s tudied the effect of gas stream temperature on the removal of NO from a gas stream, under otherwise fixed operating conditions, using the same urea-to-hydrogen peroxide molar ratio and hydrogen peroxide to NO molar ratio in each of the six temperature studies.
  • Example 3 The apparatus used for Example 3 was the same as that utilized in Examples 1 and 2.
  • Example 3 as in Example 1, the aqueous solution of the reagent was prepared by dissolution of carbamide peroxide, a solid adduct of urea and hydrogen peroxide, in water to prepare an aqueous solution that contained 5.0 wt. % carbamide peroxide, corresponding to 3.2 wt. % urea and 1.8 wt. % H 2 0 2 .
  • the molar ratio of urea to hydrogen peroxide in the aqueous reagent solution was therefore 1 : 1 urea:H 2 0 2 , as was the case in Example 1.
  • the aqueous reagent solution was introduced into the gas stream in an amount that provided 2 moles of hydrogen peroxide to each mole of NO in the inlet gas stream.
  • the ratio of urea to NO was likewise 2: 1 urea:NO.
  • Example 3 studies were carried out at six different gas stream temperatures ranging from 330°C to 545°C. [0124] Table 4 summarizes the six operating runs at gas temperatures ranging from 330°C to 545°C, with the tube reactor inlet and outlet NO concentrations being shown along with the percentage NO reduction achieved.
  • Comparative Example 4 studied the effect of using hydrogen peroxide alone, to determine its effectiveness in the removal of N O from a. ga s stream.
  • Comparative Example 4 The apparatus used for Comparative Example 4 was the same as that utilized in Example 1. In Comparative Example 4, concentrated aqueous hydrogen peroxide (50 wt. %) was dissolved in water to obtain an aqueous hydrogen peroxide solution containing 5 wt. % H 2 0 2 . [0129] The aqueous hydrogen peroxide solution was injected into the NO-containing gas stream at a rate that provided two moles H 2 O 2 per mole of NO in the gas stream.
  • the temperature of the gas stream in the tube reactor was 405°C, and the gas stream flow rate was 3.2 L/min., the latter being the same as used in Example 1.
  • N 2 is considered an environmentally benign reaction product
  • the NO 2 reaction product formed in this study using hydrogen peroxide alone as the reactant is normally considered to be an objectionable contaminant, as is NO, in a flue gas stream.
  • Example 5 was a laboratory study carried out under the similar conditions and in the same apparatus as in Comparative Examples 4 (H 2 0 2 alone) except that the reagent utilized in Example 5 was carbamide peroxide, to determine this reagent's effectiveness in the removal of NO from a gas stream.
  • Example 5 carbamide peroxide, the solid adduct of urea and hydrogen peroxide containing a mole ratio of 1: 1 urea: H 2 0 2 , was dissolved in water to obtain an aqueous solution containing 5.0 wt. % carbamide peroxide, corresponding to 3.2 wt. % urea and 1.8 wt. % H 2 0 2 .
  • Example 5 demonstrate an unexpected and very significant benefit to the use of a reagent containing carbamide peroxide in effecting conversion of NO in a gas stream to innocuous reaction products.
  • Comparative Example 6 studied the effect of using urea alone, to determine its effectiveness in the removal of NO from a gas stream.
  • Comparative Example 6 The apparatus used for Comparative Example 6 was the same as that utilized in Example 1. in Comparative Example 6, the urea (in solid form) was dissolved in water to obtain an aqueous solution containing 5 wt. % urea.
  • the aqueous urea solution was injected into the NO-containing gas stream at a rate that provided two moles urea per mole of NO in the gas stream.
  • the temperature of the gas stream in the tube reactor was 405°C.
  • the gas stream flow rate was 3.2 L/min., the same as used in Examples 1-5.
  • the results of this study found that there was essentially no change in the NO concentration between the inlet and outlet of the tube reactor, indicating that the urea alone was ineffective for removing or reducing or otherwise affecting the concentration of NO in the gas stream at 405°C.
  • the effect of urea alone on the NO reduction was negligible at 625°C.
  • Example 7 was a laboratory study that evaluated and compared the effectiveness of two reagents in the remo val of NO from NO-containing gas streams at temperatures of 625°C, 750°C and 800°C.
  • the two reagents were ( ! ) carbamide peroxide in aqueous solution and, for comparative purposes, (2) urea alone, in aqueous solution.
  • Example 7 was a carried out under the similar conditions and in the same apparatus as in Comparative Example 4 i l l ⁇ .) ' > alone) and 6 (urea alone). The gas stream flow rate was 3.2 L/min. [0151 ] In this Example 7, the reagent was obtained by dissolution of carbamide peroxide in water to obtain ars aqueous solution containing 5.0 wt. % carbamide peroxide, corresponding to 3.2 wt. % urea and 1.8 wt. % 3 ⁇ 4(3 ⁇ 4, as was done in Example 5.
  • Example 7 the comparative urea reagent was obtained by dissolution of urea (in solid form) in water to obtain an aqueous solution containing 5 wt. % urea, as was done in Comparative Example 6.
  • Negligible NO 2 was produced during this run at 625°C (see the lower curve in Figure 4), which strongly suggests that virtually all of the NO being reacted was being converted to N 2 (which was not measured). It should be noted that the overall level of ⁇ , the additive concentrations of NO and NO 2 , decreased along with the removal of NO.
  • Figure 3 shows the results of the comparative study in Example 6 using aqueous urea solution as the reagent at the same temperature of 625°C.
  • a comparison of the data in Fig. 3 and Fig. 4 shows that urea alone cannot provide reduction of NO at this temperature, whereas carbamide peroxide demonstrated a successful NO reduction.
  • Example 8 studied the effect of water concentration in the gas stream on the NO reduction efficiency. Five different molar ratios of water to reagent in the inlet gas stream were used to study the water concentration effect (relative to the carbamide peroxide) on the removal of NO from the gas stream.
  • Example 8 The apparatus used for Example 8 was the same as that utilized in Examples 1-7. [0169] In Example 8, as in Example 1, the aqueous solution of the reagent was prepared by dissolution of carbamide peroxide in water to prepare an aqueous solution that contained different concentrations of carbamide peroxide.
  • the molar ratio of urea to hydrogen peroxide in the aqueous reagent solution was therefore 1 : 1 urea:H 2 0 2 , as was the case in Example 1.
  • the aqueous reagent solution was introduced into the gas stream in an amount that provided 2.1 moles of hydrogen peroxide to each mole of NO in the inlet gas stream.
  • the ratio of urea to NO was likewise 2.1 : 1 urea:NO.
  • Example 8 studies were carried out at five different water : reagent molar ratios ranging from 5: 1 to 200: 1.
  • Table 5 summarizes the five operating runs at gas temperature of 465°C, with the water to reagent molar ratios being shown along with the percentage NO reduction achieved.
  • Reagent is carbamide peroxide
  • Example 9 studied the typical gas compositions in the reduction experiments using carbamide peroxide. For five runs at different experimental conditions the concentrations of injected urea, hydrogen peroxide, and water in the gas stream were calculated, NO concentrations in the inlet and outlet gas stream were measured and NO reduction was determined.
  • Table 6 summarizes the five runs at different conditions, with the reagent concentration of 5.0 wt%. The concentrations of the components in the gas stream are shown along with the percentage NO reduction achieved.
  • Reagent is carbamide peroxide
  • Example 10 illustrates the application of a preferred embodiment of the present invention to the ⁇ treatment of a flue gas stream from a combustion boiler utilizing high sulfur coal. The process is operated continuously, and normal steady state conditions are assumed for purposes of Example 10.
  • Figure 8 illustrates a schematic flow diagram of this preferred embodiment; reference numerals and letters in Figure 8 are included in the process description which follows. References to gaseous component concentrations in percentage (%), parts per million (ppm) or parts per billion (ppb) refer to such concentrations on a volume basis.
  • the coal used in the combustion unit of this Example 10 is high sulfur coal containing 2 wt. % sulfur.
  • the combustion furnace is operated with preheated air, and it is assumed that there is 1% conversion of the sulfur in the coal to SO 3 in flue gas from the combustion unit.
  • the exit combustion flue gas stream 1 contains about 420 ppm Ox, i.e., 400 ppm NO and about 20 ppm NO2, and also about 900 ppm SO2 and about 9 ppm SO3.
  • the combustion flue gas stream 1 is passed through a heat exchange unit (not shown in Figure 8) that reduces the temperature of the hot combustion flue gas stream 1 to about 900°F (482°C).
  • the reduced-temperature flue gas stream 1 has essentially the same composition as prior to its being subjected to a heat exchange unit operation.
  • the flue gas stream 1 is then treated in a selective non-catalytic reduction reactor A to reduce its ⁇ content.
  • the flue gas stream is reacted in the selective non-catalytic reduction (SNCR) unit operation with an aqueous reagent solution 2 that contains water and carbamide peroxide.
  • the aqueous reagent solution 2 contains 6.4 wt. % urea and 3.6 wt. % hydrogen peroxide (providing a mole ratio of 1 : 1 ureaiH ⁇ C ⁇ in the reagent solution) and is prepared (not shown in Figure 8) by dissolution of appropriate amounts of solid carbamide peroxide in water.
  • the aqueous reagent solution 2 containing water and carbamide peroxide is introduced into the flue gas stream 1 via a set of injection nozzles (not shown in Figure 8) that spray and disperse the solution into the hot flue gas stream in the SNCR reaction apparatus A.
  • Sufficient aqueous reagent solution 2 is introduced into the flue gas stream 1 in the SNCR reactor A to provide 2 moles of urea per mole NO in the flue gas stream.
  • the amount of urea in the injected aqueous reagent solution 2 thus provides a stoichiometric amount of urea required to react with the NO that is contained in the flue gas stream 1.
  • the reduction reaction of the urea - hydrogen peroxide reagent solution 2 with ⁇ in the flue gas steam 1 in the SNCR reactor A reduces the NO content of the flue gas stream 2, producing N 2 , CO 2 and water in the flue gas stream 3 that exits the SNCR reactor A.
  • the flue gas stream 3 exiting from the SNCR unit operation A contains about 900 ppm SO 2 and about 9 ppm SO 3 and reduced levels of ⁇ , about 150 ppm ⁇ .
  • the flue gas stream 3 exiting from the SNCR reactor A is directed to one or more electrostatic precipitators (ESP), shown as block B labeled as ESP in Figure 8, to remove entrained solids, i.e., particulates such as fly ash from the coal combustion, from the flue gas stream 3.
  • ESP electrostatic precipitators
  • the solids-free ESP-treated flue gas exits the electrostatic precipitator operation B as flue gas stream 4.
  • the ESP solids, removed as stream 5, are disposed of in a landfill.
  • the ESP-treated flue gas stream 4 has a reduced ⁇ content, as compared with the combustion flue gas stream 1 upstream of the SNCR reactor A: the flue gas stream 4, downstream of the ESP operation B, contains about 150 ppm ⁇ , compared to about 420 ppm ⁇ in the untreated combustion flue gas stream 1 upstream of the SNCR reactor A.
  • the SOx-containing flue gas stream 4 exiting from the ESP operation B is next subjected to a wet scrubbing desulfurization procedure (not shown in Figure 8) to reduce its SO2 and SO3 content before the flue gas stream 4 is vented to the atmosphere.
  • Wet desulfurization scrubbing operations using an alkali such as lime, limestone or soda ash, are well known procedures for desulfurizing SOx-containing flue gas streams.

Landscapes

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

Abstract

Procédé d'élimination des oxydes d'azote dans des flux de gaz de combustion de sources fixes, par introduction d'un réactif ou d'un mélange contenant du peroxyde de carbamide et de l'eau comme agent réducteur.
EP14843945.8A 2013-09-13 2014-09-15 Traitement des oxydes d'azote dans les flux de gaz de combustion Withdrawn EP3043890A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201314026338A 2013-09-13 2013-09-13
PCT/US2014/055630 WO2015039019A1 (fr) 2013-09-13 2014-09-15 Traitement des oxydes d'azote dans les flux de gaz de combustion

Publications (2)

Publication Number Publication Date
EP3043890A1 true EP3043890A1 (fr) 2016-07-20
EP3043890A4 EP3043890A4 (fr) 2017-04-26

Family

ID=56116141

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14843945.8A Withdrawn EP3043890A4 (fr) 2013-09-13 2014-09-15 Traitement des oxydes d'azote dans les flux de gaz de combustion

Country Status (2)

Country Link
EP (1) EP3043890A4 (fr)
CN (1) CN106559989A (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109289506A (zh) * 2018-10-22 2019-02-01 湘潭大学 一种催化脱除氮氧化物脱硝剂
CN111514716B (zh) * 2020-06-04 2023-10-20 深圳市爱诺实业有限公司 烟气脱硫、脱氮、脱汞净化方法和设备

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5314662A (en) * 1976-07-28 1978-02-09 Hitachi Ltd Method for decreasing nitrogen oxides concentration of combustion exhaust gas
JP3558737B2 (ja) * 1995-06-08 2004-08-25 バブコック日立株式会社 排ガス脱硝方法と排ガス処理方法
RU2314861C1 (ru) * 2006-07-10 2008-01-20 Федеральное агентство по образованию Российский государственный университет нефти и газа им. И.М.Губкина Способ селективной некаталитической очистки дымовых газов от оксидов азота
RU2403081C1 (ru) * 2009-06-30 2010-11-10 Государственное образовательное учреждение высшего профессионального образования Российский государственный университет нефти и газа им. И.М. Губкина Способ некаталитической очистки дымовых газов от оксидов азота

Also Published As

Publication number Publication date
EP3043890A4 (fr) 2017-04-26
CN106559989A (zh) 2017-04-05

Similar Documents

Publication Publication Date Title
US9114357B2 (en) Treatment of nitrogen oxides in flue gas streams
CA2760777C (fr) Traitement des nox presents dans les gaz de carneau
EP3057682B1 (fr) Procédé et appareil pour enlever les oxydes d'azote de gaz d'échappement
US5670122A (en) Methods for removing air pollutants from combustion flue gas
EP1570894B1 (fr) Procédé et appareil pour l'élimination des émissions de mercure de la combustion de charbon
EP0860197B1 (fr) Procédé et dispositif pour le traitement de gaz d'échappement
CA2769641C (fr) Activation de compose reactif par catalyseur
US8980207B1 (en) Method and system for removal of mercury from a flue gas
WO2014041951A1 (fr) Système de traitement du mercure contenu dans un gaz d'échappement
EP3043890A1 (fr) Traitement des oxydes d'azote dans les flux de gaz de combustion
Pfeffer et al. Combustion flue gas NO x treatment

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20160413

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIN1 Information on inventor provided before grant (corrected)

Inventor name: BLOCK, PHILIP A.

Inventor name: HOLTZ, TIMOTHY

Inventor name: ROVISON, JOHN M. JR.

Inventor name: PISANOVA, ELENA

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20170324

RIC1 Information provided on ipc code assigned before grant

Ipc: B01D 53/78 20060101AFI20170320BHEP

Ipc: B01D 47/06 20060101ALI20170320BHEP

Ipc: B01D 53/56 20060101ALI20170320BHEP

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

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

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20171024