WO2019156379A1 - Catalyseur pour la réduction d'oxyde d'azote et son procédé de production - Google Patents

Catalyseur pour la réduction d'oxyde d'azote et son procédé de production Download PDF

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WO2019156379A1
WO2019156379A1 PCT/KR2019/000653 KR2019000653W WO2019156379A1 WO 2019156379 A1 WO2019156379 A1 WO 2019156379A1 KR 2019000653 W KR2019000653 W KR 2019000653W WO 2019156379 A1 WO2019156379 A1 WO 2019156379A1
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catalyst
nitrogen oxides
copper
formula
nitrogen oxide
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PCT/KR2019/000653
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English (en)
Korean (ko)
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김종식
하헌필
변지영
김상훈
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한국과학기술연구원
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Priority claimed from KR1020180015237A external-priority patent/KR102068063B1/ko
Priority claimed from KR1020180084065A external-priority patent/KR102187494B1/ko
Application filed by 한국과학기술연구원 filed Critical 한국과학기술연구원
Publication of WO2019156379A1 publication Critical patent/WO2019156379A1/fr

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    • 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
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • 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
    • B01D53/90—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
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8472—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters

Definitions

  • the present invention relates to a catalyst for reducing nitrogen oxides and a nitrogen oxide reduction system using the same. More particularly, the present invention relates to a nitrogen oxide reduction catalyst including copper vanadate and a nitrogen oxide reduction system using the same, which are used in a selective catalytic reduction (SCR) process.
  • SCR selective catalytic reduction
  • the present invention also relates to a catalyst for reducing nitrogen oxides treated with sulfates and a method for preparing the same. More specifically, the surface of the catalyst included in the selective catalytic reduction of nitric oxide by NH3 and NH3-SCR, which applies ammonia (NH3) as a reducing agent, is used to reduce the performance of nitrogen oxides by improving sulfate performance. It relates to a catalyst and a preparation method thereof.
  • the present invention relates to a catalyst production method for improving the surface properties by initially modifying the surface of the catalyst by controlling the pH of the aqueous solution used in the production process of the catalyst for reducing nitrogen oxides.
  • One of the effective methods for this is the process of converting nitrogen oxides into nitrogen and water vapor using ammonia as a reducing agent (selective catalytic NO x reduction by NH 3 , NH 3 -SCR).
  • selective catalytic NO x reduction by NH 3 , NH 3 -SCR selective catalytic NO x reduction by NH 3 , NH 3 -SCR.
  • SCR selective catalytic NO X reduction
  • NH 3 another precursor of ultra-fine dust formation
  • it releases environmentally friendly nitrogen (N 2 ) and water vapor (H 2 O) it is commercialized to expand its scope of application.
  • NH 3 is used as a reducing agent, and research on the active site of a solid catalyst having high activity and stability in the turnover cycle of nitrogen oxide (NO X ) is the most important area.
  • the following chemical schemes represent the reaction of NO x reduction in the SCR process.
  • the core for the efficient progress of the NH 3 -SCR is by the implementation of a suitably modified catalyst surface in the NH 3 -SCR unit (unit) is attached / applied field, which may be formed through the surface treatment after the catalyst preparation.
  • a suitably modified catalyst surface in the NH 3 -SCR unit (unit) is attached / applied field, which may be formed through the surface treatment after the catalyst preparation.
  • the catalyst is applied in the NH 3 -SCR, it must achieve a broad NH 3 -SCR unit (unit) high NOx conversion rates at the operating temperature (NO X conversion) and high nitrogen selectivity (N 2 selectivity).
  • Alkali-metals such as Na or K in the fly ash of the power plant, one of the compounds that may affect the durability of the catalyst, may be subjected to NH 3 -SCR progression. It may be mixed with a feed gas for supply to the catalyst surface. These alkali metal species poison the activated acid (Bronsted acid or Lewis acid sites) on the catalyst surface during the NH 3 -SCR reaction, which is a major cause of lowering the conversion of nitrogen oxides.
  • Thermal aging which is one of the factors that lowers the durability of the catalyst, causes gradual agglomeration of the active surface and the promoter particles on the surface of the catalyst during prolonged driving of a diesel vehicle. This is a major cause of lowering the conversion of nitrogen oxides contained in the exhaust gas of automobiles, since NH 3 or NO X reduces the surface density of accessible active sites / catalysts.
  • vanadate based catalysts In order to overcome the problems of the conventional catalysts containing iron (Fe) or copper (Cu) as active sites, vanadate based catalysts have been proposed.
  • vanadate-based catalyst 1) it can have an excellent catalyst life (longevity) compared to zeolites, and 2) vanadium crystals when including a metal such as cerium (Ce), iron (Fe) or copper (Cu)
  • Ce cerium
  • Fe iron
  • Cu copper
  • the present invention is to solve various problems including the above problems, Cu-rich copper vanadate crystal grains containing a large amount of copper (for example, Cu 3 V 2 O 8 , Cu 5 V 2 O 10 ) to prepare a catalyst, to achieve an active site (active site) having a high nitrogen oxide (NO X ) conversion and high nitrogen (N 2 ) selectivity.
  • an object of the present invention is to create an additional active site on the surface of the catalyst and to improve the resistance and resistance of sulfur or sulfur dioxide to the poisoning of the catalyst surface (poisoning) to improve the performance and lifetime of the nitrogen oxide reduction system.
  • a catalyst in which oxides of Group 15 or Group 16 elements of the periodic table are incorporated into a promoter including copper vanadate (Cu 3 V 2 O 8 or Cu 5 V 2 O 10 ) as an active point, and a nitrogen oxide reduction reaction system using the same shows improved NH 3 -SCR performance and durability for SO 2 / ABS compared to commercial catalyst (V 2 O 5 -WO 3 / TiO 2 ) having a similar V content.
  • the present invention improves the NH 3 -SCR reaction performance by further improving the surface properties of the catalyst (for example, Cu 3 V 2 O 8 -Sb / TiO 2 ), enhance the durability of the catalyst to SO 2 / ABS, It is an object to improve the durability of the catalyst against alkali metal species and degradation.
  • the catalyst for example, Cu 3 V 2 O 8 -Sb / TiO 2
  • the present invention by controlling the pH of the aqueous solution used in the catalyst manufacturing process to modify the surface of the catalyst initially to improve the surface properties, improve the reaction performance of the catalyst, and to improve the durability.
  • a promoter containing an oxide of a group 15 or group 16 element, copper vanadate crystals represented by the following [Formula 1] crystal Provided is a catalyst for reducing nitrogen oxides, including particles and a carrier on which the copper vanadate crystal grains and the promoter are supported.
  • X is an integer having a value of 3 or 5.
  • the catalyst may have a porous structure on the surface.
  • the copper vanadate crystal grains may have a diameter of 0.1 nm to 500 ⁇ m.
  • the Group 15 or Group 16 elements are nitrogen (N), phosphorus (P), sulfur (S), arsenic (As), selenium (Se), antimony (Sb) , At least one selected from the group consisting of tellurium (Te), bismuth (Bi), polonium (Po), Moscow (Mc), and liver morium (Lv).
  • the carrier is any one of carbon (C), Al 2 O 3 , MgO, ZrO 2 , CeO 2 , TiO 2 and SiO 2 , compared to 100 parts by weight of the carrier
  • the promoter may include 10 ⁇ 4 to 50 parts by weight
  • the copper vanadate salt crystal particles may include 10 ⁇ 4 to 50 parts by weight based on 100 parts by weight of the carrier.
  • the catalyst for reducing nitrogen oxides may be sulfided on the surface of the catalyst for 0.1 hour to 24 hours in the temperature range of 200 °C to 800 °C.
  • the catalyst is a catalyst for reducing nitrogen oxides, a reducing agent ammonia (NH 3 ) and nitrogen oxides (NO X )
  • a nitrogen oxide reduction system in which a reaction fluid comprising a molar ratio of 1: 1 is injected to reduce the nitrogen oxides.
  • the nitrogen oxide reduction system includes a catalyst of 0.1 g to 10 g, the particles of the catalyst may have a diameter of 1 ⁇ m to 1,000 ⁇ m.
  • the reaction fluid, the concentration of the ammonia and the nitrogen oxide may be each 100ppm or more.
  • reaction fluid may further include oxygen gas (O 2 ), water vapor (H 2 O) or sulfur dioxide (SO 2 ).
  • O 2 oxygen gas
  • H 2 O water vapor
  • SO 2 sulfur dioxide
  • the reaction fluid may be injected at a space velocity of 1,000 hr ⁇ 1 or more in a temperature range of 150 ° C. to 800 ° C.
  • X is an integer having a value of 3 or 5.
  • the catalyst may have a porous structure on the surface.
  • the copper vanadate salt crystal particles may have a diameter of 0.1 nm to 500 ⁇ m.
  • the Group 15 or Group 16 elements nitrogen (N), phosphorus (P), sulfur (S), arsenic (As), selenium (Se), antimony (Sb) It may be any one or more combinations selected from the group consisting of, tellurium (Te), bismuth (Bi), polonium (Po), Moscow (Mc) and liver morium (Lv).
  • the carrier is any one of carbon (C), Al 2 O 3 , MgO, ZrO 2 , CeO 2 , TiO 2 and SiO 2 , compared to 100 parts by weight of the carrier
  • the promoter may include 10 -4 to 50 parts by weight
  • the iron vanadate salt crystal particles may include 10 -4 to 50 parts by weight based on 100 parts by weight of the carrier.
  • a promoter containing an oxide (oxide) of the group 15 or 16 elements, copper vanadate salt crystal particles and the carrier represented by the following [Formula 1]
  • a method of preparing a catalyst for reducing nitrogen oxides comprising the steps of preparing a catalyst comprising the same and sulphating the copper vanadate crystal grains, wherein the catalyst for reducing nitrogen oxides is the copper vanadium salt crystal grains and the catalyst.
  • the promoter is supported on the carrier, and the copper vanadate salt crystal particles are provided with a method for producing a catalyst for reducing nitrogen oxides in which copper sulfate or vanadium sulfate are formed on at least part of a surface thereof.
  • X is an integer having a value of 3 or 5.
  • the sulfation process is SO 2 and O is performed by the reaction gas comprising 2, the concentration of SO 2 and O 2 in the reaction gas is in the range of 10ppm to 10 5 ppm It can have
  • the flow rate (flow rate) of the reaction medium has a range of 10 -5 mL min -1 to 10 5 mL min -1
  • the pressure of the reactor is 10 -5 bar To 10 5 bar.
  • the sulfidation treatment may be performed for 0.1 to 24 hours in the temperature range of 200 °C to 800 °C.
  • an active site corresponding to (1) or (2) below;
  • a promoter comprising one species or a combination thereof selected from oxides of group 15 or 16 elements;
  • a support including the active point and the promoter, wherein at least a portion of the surface of the catalyst is provided with a copper oxide or vanadium sulfate.
  • X is an integer having a value of 3 or 5.
  • the active point may include monoclinic Cu 3 V 2 O 8 .
  • the active point may include all of the tetragonal V 2 O 5 and monoclinic CuO.
  • the surface of the catalyst may have a porous structure.
  • the diameter of the active point may be 0.1 nm to 500 ⁇ m.
  • the Group 15 or Group 16 elements nitrogen (N), phosphorus (P), sulfur (S), arsenic (As), selenium (Se), antimony (Sb) , At least one selected from the group consisting of tellurium (Te), bismuth (Bi), polonium (Po), Moscow (Mc), and liver morium (Lv).
  • the support may include any one of carbon (C), Al 2 O 3 , MgO, ZrO 2 , CeO 2 , TiO 2 and SiO 2 .
  • the promoter may include 10 -4 to 50 parts by weight relative to 100 parts by weight of the carrier.
  • the active point may include 10 -4 to 50 parts by weight based on 100 parts by weight of the carrier.
  • the carrier may be TiO 2 having an anatase phase.
  • preparing a mixed solution containing a vanadium precursor and a copper precursor Adjusting a pH after adding a substance constituting the support to the mixed solution;
  • a method for preparing a catalyst for reducing nitrogen oxides comprising calcining a solid obtained after dehydration of the mixed solution to prepare a catalyst for reducing nitrogen oxides including an active site in a carrier.
  • the step of adjusting the pH to adjust the pH to 5 or less to prepare an active point corresponding to (1) below, or to adjust the pH greater than 5 to prepare an active point corresponding to (2) below It may include.
  • X is an integer having a value of 3 or 5.
  • the step of adjusting the pH is an acidic aqueous solution containing one or more combinations selected from HCl, H 2 SO 4 , HNO 3 , acetic acid, oxalic acid, tartaric acid or the like or It may be to add a basic aqueous solution containing one or more combinations selected from NH 4 OH, NaOH, Ca (OH) 2 , Mg (OH) 2 and the like.
  • the material constituting the carrier may be one or more of group 15 or group 16 elements are mixed.
  • the material constituting the support may include any one of carbon (C), Al 2 O 3 , MgO, ZrO 2 , CeO 2 , TiO 2 and SiO 2 . have.
  • the vanadium precursor is NH 4 VO 3 , NaVO 3, VCl 2 , VCl 3 , VBr 3 , VCl 3 3C 4 H 8 O, VO (C 5 H 7 O 2 ) 2 , VO (OC 2 H 5) 3, VC 10 H 10 C l2, VC 18 H 14 I, VOCl 3, VOF 3, VO (OCH (CH 3) 2) 3, V (C 5 H 7 O 2) 3 , VOSO 4 , V (C 5 H 5 ) 2 .
  • the copper precursor is CuSO 4 , Cu (NO 3 ) 2 , CuF 2 , CuCl 2 , CuBr, CuBr 2 , CuI, CuSCN, Cu (BF 4 ) 2 , Cu (ClO 4 ) 2 , Cu (OH) 2 , Cu (NH 3 ) 4 SO 4 , Cu 2 P 2 O 7 , Cu [-CH (OH) CO 2 ] 2 , Cu (CO 2 CH 3 ) 2 , CuCN, Cu (CF 3 SO 3 ) 2 , C 6 H 5 SCu, C 8 H 4 CuO 4 , C 9 H 4 CuNS, C 10 H 6 CuN 4 O 4 , C 10 H 20 CuN 4 O 8 , C 10 H 14 NO 3 1 / 2Cu C 12 H 22 CuO 14 , Cu (C 9 H 6 NO) 2 , C 14 H 8 CuF 2 O 8 S 2 , C 14 H 12 CuO 5 , C 24 H 14 C l4 CuN 4 O 2 ,
  • the sulfuric acid treatment step of exposing a process gas containing sulfur dioxide (SO 2 ) and oxygen (O 2 ) to the surface of the catalyst may be further included.
  • the concentration of SO 2 and O 2 contained in the treatment gas may be in the range of 10-5 ppm to 10 5 ppm, respectively.
  • the flow rate (flow rate) is 10 -5 mLmin -1 to 10 5 mLmin -1
  • the pressure is 10 -5 bar to 10 5 bar Can be.
  • the treatment step may be performed for 0.1 to 24 hours at a temperature of 200 °C to 800 °C.
  • Cu-rich copper vanadate-based crystal grains containing a large amount of copper for example, Cu 3 V 2 O 8 or Cu 5 V
  • a catalyst surface having high NO x conversion and high N 2 selectivity.
  • the copper vanadate-based crystal grains (Cu 3 V 2 O 8 or Cu 5 V 2 O 10 ) and oxides of group 15 or 16 of the periodic table Promoters comprising a prepared catalyst (dispersed in the carrier), and the surface of the catalyst may be sulfated to improve the performance of the catalyst for reducing nitrogen oxides.
  • the present invention by the sulfate treatment of the surface of the catalyst to improve the active acid point (for example, Bronsted acid site) and oxidation / reduction characteristics (redox feature) to improve the NH 3 -SCR reaction performance, SO 2 It is possible to improve the durability of the catalyst against / ABS, alkali metal species and degradation.
  • active acid point for example, Bronsted acid site
  • oxidation / reduction characteristics redox feature
  • TEM transmission electron microscope
  • FIG. 2 is a graph showing a binary diagram of copper vanadate according to an embodiment of the present invention.
  • FIG. 3 is a schematic diagram illustrating an SCR system according to an embodiment of the present invention.
  • XRD patterns X-ray diffraction patterns
  • FIG. 5 is a graph showing selected area electron diffraction patterns (SAED patterns) of a catalyst including copper vanadate crystal particles according to an embodiment of the present invention.
  • 6 to 8 are graphs showing performance analysis results of the SCR system according to the embodiment and the comparative example of the present invention.
  • FIG 9 is a graph showing the change in nitrogen oxide (NO X ) conversion rate of the SCR system according to the embodiment and the comparative example of the present invention.
  • FIG. 10 is a graph showing X-ray diffraction (XRD) patterns of catalysts and SO Y 2 -functionalized catalysts according to Comparative Examples and Examples of the present invention.
  • FIG. 11 is a high resolution transmission electron microscopy (HRTEM) photograph of a catalyst and SO Y 2 -functionalized catalysts according to Comparative Examples and Examples of the present invention.
  • HRTEM transmission electron microscopy
  • FIG. 12 is a photograph showing an X-ray photoelectron (XP) spectra under the O 1s region of a catalyst and SO Y 2 -functionalized catalysts according to Comparative Examples and Examples of the present invention.
  • XP X-ray photoelectron
  • FIG. 20 is a graph showing the SO 2 / O 2 atmosphere and background-subtracted in-situ diffuse reflectance infrared Fourier transform (DRIFT) spectra of the catalysts prepared in Examples 11 to 13 of the present invention at 500 ° C.
  • DRIFT diffuse reflectance infrared Fourier transform
  • 21 is a graph showing the results of NH 3 -SCR performance analysis in the presence of H 2 O of the catalysts prepared in Examples 11 to 13.
  • the present invention relates to a nitrogen oxide reduction catalyst comprising copper vanadate crystal grains and a nitrogen oxide reduction system using the same.
  • Reduction of nitrogen oxides (NO X ) can be carried out by the chemical reaction formula of the following formula (1) and (2).
  • a catalyst for reducing nitrogen oxides may be used to improve the reaction efficiency and reaction rate of nitrogen monoxide (NO X ) and nitrogen dioxide (NO 2 ) as a reactant and ammonia (NH 3 ) as a reducing agent.
  • NO X nitrogen monoxide
  • NO 2 nitrogen dioxide
  • NH 3 ammonia
  • the catalyst for reducing nitrogen oxides is a promoter including an oxide of group 15 or group 16 elements, copper vanadate represented by the following [Formula 1] (Copper vanadate) Crystal particles and copper vanadate salt crystals and may include a carrier on which the promoter is supported.
  • X is an integer having a value of 3 or 5.
  • 1 is a transmission electron microscope (TEM) photograph showing a catalyst for reducing nitrogen oxides according to an embodiment of the present invention.
  • 1 (a) is a photograph showing Cu 3 V 2 O 8 as a catalyst for reducing nitrogen oxides according to an embodiment of the present invention, and (b) of FIG. 1 shows Cu 5 V 2 O 10 .
  • the proposed catalyst for reducing nitrogen oxides may include copper vanadate crystal grains and Cu-rich copper vanadate containing a large amount of copper.
  • the copper vanadate may include, for example, Cu 3 V 2 O 8 (Cu 3 O 3 -V 2 O 5 ), Cu 5 V 2 O 10 (Cu 5 O 5 -V 2 O 5 ), and the like. .
  • FIG. 2 is a graph showing a binary diagram of copper vanadate according to an embodiment of the present invention. According to FIG. 2, copper vanadium salts can be seen in various phases of. In order to improve the NO x conversion and N 2 selectivity of the nitrogen oxide reduction reaction, the present invention applies the copper copper vanadate crystal grains as an active site of the catalytic reaction.
  • the active site of the catalyst is used to easily adsorb the ammonia (NH 3 ) of the base as a reducing agent and to smoothly convert to N 2 and H 2 O based on the interaction with NO X. It must have a large amount of acid site density.
  • NOC selective catalytic reduction
  • NO X nitrogen oxides
  • -ONH 4 or 2 ammonia salt
  • a copper vanadate used as a conventional catalyst since it is formed based on VO 6 having an octahedral crystal structure, it can provide only coordinatively saturated V-sites with coordination bonds. Can be.
  • the supercopper vanadate crystal grains of the present invention it is formed based on VO 4 having a tetrahedral crystal geometry to provide coordinatively unsaturated V-sites in coordination bonds. Can be.
  • CuV 2 O 6 has a higher melting point.
  • the melting point of CuV 2 O 6 is about 640 ° C. or lower, while for copper covanadium salts, it has a melting point of 760 ° C. or higher. This can prevent the emission of toxic vanadium (V) vapor and the aggregation of vanadium active sites during the SCR reaction. Therefore, using a copper copper vanadate crystal grains as the active site of the SCR reaction, it is possible to produce a catalyst having a high NO X conversion and N 2 selectivity.
  • the catalyst for reducing nitrogen oxides may be configured in a morphology having a characteristic of a large surface area.
  • the wider the surface area of accelerating the adsorption of the reactants NOx or ammonia, to increase the reaction rate may increase the nitrogen oxide (NO X) reduction efficiency.
  • the catalyst may have a porous structure.
  • a porous structure having a large surface area can be realized by configuring the carrier as an aggregate aggregated by calcining the powder material.
  • the copper vanadate crystal grains may have a porous rough surface structure, and may have a diameter of 0.1 nm to 500 ⁇ m.
  • the catalyst for reducing nitrogen oxides may include a promoter including an oxide of a group 15 or group 16 element.
  • the active site of the catalyst for reducing nitrogen oxides needs to have low activity in adsorption of sulfur dioxide (SO 2 ) contained in flue gas and oxidation reaction of sulfur dioxide (SO 2 ).
  • Ammonia a reducing agent, is reacted with sulfur trioxide by the chemical reaction formulas of the following formulas (3) to (5) to form ammonium sulfate (ammonium sulfate or ammonium bisulfate) on the surface of the catalyst, and ammonium sulfate is a catalyst of It can adsorb irreversibly to the active site.
  • the adsorbed ammonium sulfate can reduce the activity of the catalyst by preventing the adsorption of nitrogen oxides (NO X ) and ammonia, a reducing agent.
  • sulfur trioxide (SO 3 ) formed by oxidizing sulfur dioxide may combine with water vapor contained in the flue gas to generate sulfuric acid (H 2 SO 4 ) and cause a problem of corroding the system after the SCR process.
  • a promoter including an oxide of a group 15 or group 16 element included in the catalyst for reducing nitrogen oxides may reduce the binding energy between sulfur dioxide (SO 2 ) and the surface of the catalyst. have. This may minimize the oxidation of sulfur dioxide (SO 2 ) that may occur during the low temperature SCR reaction. In other words, sulfur dioxide and ammonia react with each other to minimize the amount of ammonium sulfate adsorbed on the surface of the catalyst to reduce the activity of the catalyst or to prevent the problem of corrosion caused by sulfuric acid. Accordingly, the catalyst for reducing nitrogen oxides may have resistance to sulfur or sulfur dioxide (SO 2 ) poisoning, including a promoter, and may further provide an acid site as an active site.
  • Group 15 or Group 16 elements are nitrogen (N), phosphorus (P), sulfur (S), arsenic (As), selenium (Se), antimony (Sb), tellurium (Te), bismuth (Bi), polonium (Po), moskovium (Mc) and liver morium (Lv), or at least one selected from the group consisting of, and preferably, antimony oxide (Sb-oxide). May be).
  • the catalyst for reducing nitrogen oxides may include a carrier on which copper vanadate crystal particles and a promoter are supported.
  • the active site of the catalyst should have a large redox characteristic in order to facilitate the adsorption and conversion of nitrogen oxides (NO X ). This is because the SCR cycle of nitrogen oxides involves a redox reaction with oxygen (O 2 ) to remove the -ONO groups adsorbed at the active sites on the catalyst surface.
  • Oa highly reactive oxygen
  • the catalyst when the catalyst is prepared by supporting the copper vanadate crystal grains on an appropriate carrier, it is possible to smoothly supply the highly reactive oxygen (Oa) species present in the carrier to the active site. That is, the redox characteristic of the catalyst can be improved.
  • the copper vanadate crystal grains can be produced in the form of high dispersion in the carrier, the catalyst efficiency can be further improved. Therefore, it is possible to manufacture a catalyst for reducing nitrogen oxides, including a carrier having the characteristics of providing the above environment.
  • the carrier is carbon (C), Al 2 O 3 , MgO, ZrO 2, and CeO 2, TiO 2 and SiO 2 any one of carrier 100 parts by weight compared to oxide 10 - It includes 4 to 50 parts by weight, the copper vanadate crystal grains relative to 100 parts by weight of the carrier may comprise 10 -4 to 50 parts by weight.
  • the catalyst for reducing nitrogen oxides is a promoter including an oxide of group 15 or group 16 elements, copper vanadate represented by the following [Formula 1] (copper vanadate) Crystal particles and copper vanadate salt crystal particles and the carrier on which the promoter is supported, the copper vanadate crystal particles may be sulfated to form copper sulfate or vanadium sulfate on at least a portion of the surface.
  • X is an integer having a value of 3 or 5.
  • the present invention relates to copper vanadate crystal particles, for example, Cu 3 V 2 O 8 or Cu 5 V 2 O 10, which are catalysts for NH 3 -SCR.
  • the surface is sulfated to relate functionalization with SO Y 2- where Y is an integer of 3 or 4.
  • Functionalization of the catalyst with SO Y 2- can provide a catalyst surface advantageous for adsorption and conversion of nitrogen oxides during the NH 3 -SCR reaction, and can improve the performance of the NH 3 -SCR reaction relative to the non-functionalized catalyst.
  • functionalization of the catalyst with SO Y 2- may increase the durability against alkali metal species and degradation phenomena during NH 3 -SCR reactions.
  • a method for producing a catalyst for reducing nitrogen oxides includes a promoter including an oxide of group 15 or group 16 elements, copper vanadate salt crystal particles represented by the following [Formula 1], and A method of preparing a catalyst for reducing nitrogen oxides, comprising the steps of preparing a catalyst comprising a support and sulphating copper vanadate crystal grains, wherein the catalyst for reducing nitrogen oxides includes copper vanadate salt crystal particles and a promoter. Is supported on the carrier, and the copper vanadate crystal grains may form copper sulfate or vanadium sulfate on at least a part of the surface.
  • X is an integer having a value of 3 or 5.
  • a catalyst including a promoter, copper vanadate crystal grains and a support is prepared.
  • the proposed catalyst for reducing nitrogen oxides may include copper vanadate crystal grains.
  • it may include Cu-rich copper vanadate containing a large amount of copper.
  • Cu-rich copper vanadates refer to vanadates (V 2 O 5 ) containing a large amount of CuO having stoichiometry, for example, Cu 3 V 2 O 8 (Cu 3 O 3 -V 2 O 5 ), Cu 5 V 2 O 10 (Cu 5 O 5 -V 2 O 5 ) and the like.
  • Sulfation treatment means functionalization of the catalyst by SO Y 2- .
  • “functionalization” may mean a process of improving the performance of the catalyst by increasing the number of active points of the catalyst or improving characteristics such as adsorption of the reactants and the catalyst.
  • the catalyst for reducing nitrogen oxides of the present invention is sulfated to be functionalized by SO Y 2 ⁇ , the catalyst surface advantageous for adsorption and conversion of nitrogen oxides can be realized, and a new active point can be formed. .
  • the sulfation process of the catalyst surface can be controlled the characteristic of the SO coupling inherent to the Y SO 2- species combined with the metal species on the surface via a functionalized by Y SO 2-.
  • SO Y 2- species present on the surface of the catalyst when the ionic character (ionic character), and the metal species of the catalyst in the form of a bi-dentate binding (bi-dentate binding), the characteristics of the covalent bond ( In the case of having a covalent character, it binds to the metal species of the catalyst in the form of mono-dentate binding.
  • the NH 3 -SCR reactivity of the catalyst may depend.
  • the sulfidation treatment may be performed by a reactor body including SO 2 and O 2 .
  • the concentration of SO 2 and O 2 ranges from 10 ppm to 10 5 ppm
  • the flow rate is 10 -5 mL min -1 to 10 5 mL min -1
  • the pressure is 10 -5 bar to 10 5 bar.
  • the sulfidation treatment may be performed for 0.1 hours to 24 hours in the temperature range of 200 °C to 800 °C.
  • the SO Y 2 -functionalization effect of the catalyst may be insufficient.
  • NO 2 for the fast NH 3 -SCR reaction of formula (7) to increase the redox characteristics of the NH 3 -SCR reaction by excessive functionalization of the carrier surface Oxygen species (O ⁇ ) that increase the production efficiency of can be extinguished. Therefore, the sulfidation treatment of the catalyst can be carried out within the range of the above-described conditions.
  • the catalyst is SO Y 2- -NH 4 Form additional species. That is, SO Y 2- species become Bronsted acid sites that can adsorb ammonia (NH 3 ) as a reducing agent. That is, the sulfated functionalized catalyst according to the present invention can increase the number of reaction active sites compared to the non-functionalized catalyst.
  • the catalyst modified by the functionalization using SO Y 2- can further form metal-SO Y 2- species to increase the oxidation / reduction properties compared to the non-functionalized catalyst.
  • the metal-SO Y 2- species can improve the production efficiency of NO 2 for the fast NH 3 -SCR reaction of the formula (7).
  • the catalyst for reducing nitrogen oxides according to the present invention can implement a catalyst surface advantageous for adsorption and conversion of ammonia / nitrogen oxides by SO Y 2 -functionalization through a sulfate treatment.
  • the surface of the catalyst is sulfated to improve the active acid point (for example, Bronsted acid site) and oxidation / reduction characteristics (redox feature) to improve NH 3 -SCR reaction performance, SO 2 / ABS, It is possible to improve the durability of the catalyst against alkali metal species and degradation.
  • the SO Y 2 -functionalization further provides 1) a desirable acid point for NH 3 -SCR on the surface of the catalyst, 2) improves the redox properties of the catalyst surface, or 3) provides a very strong binding force with alkaline compounds.
  • Eggplants can minimize the distribution of acid points, improve tolerance to alkali metals, or 4) improve resistance to hydrothermal reactions to hydrothermal aging during NH 3 -SCR reactions. It is possible to increase the durability.
  • the pH of the catalyst preparation solution may be adjusted. This is because nucleation and nucleation rates of copper oxide, vanadium oxide, or copper vanadium salt may vary under different pH conditions.
  • the pH is adjusted using an acidic or basic aqueous solution
  • the acidic aqueous solution is HCl, H 2 SO 4 , HNO 3 , acetic acid (oxalic acid), oxalic acid, tartaric acid (tartaric acid) and the like, and may be composed of one or more combinations
  • the basic aqueous solution is one or more combinations selected from NH 4 OH, NaOH, Ca (OH) 2 , Mg (OH) 2, and the like. It may be configured as.
  • the pH control range is 10 -5 to 14
  • the stirring time of the catalyst preparation solution after pH adjustment may be 10 -1 hour to 10 2 hours.
  • the stirring time of the catalyst preparation solution is 10 -1 hours or less, the pH adjustment effect may be insignificant, and when the stirring time is 10 2 hours or more, the carrier may be decomposed. Therefore, pH control of the catalyst preparation solution should be carried out within the above-described conditions.
  • a mixed solution containing a vanadium precursor and a copper precursor is prepared.
  • the vanadium precursor solution may be, for example, a solution in which a vanadium compound is dissolved in a solvent.
  • the vanadium compound is NH 4 VO 3 , NaVO 3, VCl 2 , VCl 3 , VBr 3 , VCl 3 ⁇ 3C 4 H 8 O, VO (C 5 H 7 O 2 ) 2 , VO (OC 2 H 5 ) 3 , VC 10 H 10 C l2, VC 18 H 14 I, VOCl 3, VOF 3, VO (OCH (CH 3) 2) 3, V (C 5 H 7 O 2) 3, VOSO 4, V (C 5 H 5 ) 2 lights Include.
  • the copper precursor solution may be, for example, a solution in which a copper compound is dissolved in a solvent.
  • the copper compound used as the copper precursor is CuSO 4 , Cu (NO 3 ) 2 , CuF 2 , CuCl 2 , CuBr, CuBr 2 , CuI, CuSCN, Cu (BF 4 ) 2 , Cu (ClO 4 ) 2 , Cu ( OH) 2 , Cu (NH 3 ) 4 SO 4 , Cu 2 P 2 O 7 , Cu [-CH (OH) CO 2 ] 2 , Cu (CO 2 CH 3 ) 2 , CuCN, Cu (CF 3 SO 3 ) 2, C 6 H 5 SCu, C 8 H 4 CuO 4, C 9 H 4 CuNS, C 10 H 6 CuN 4 O 4, C 10 H 20 CuN 4 O 8, C 10 H 14 NO 3 ⁇ 1 / 2Cu C 12 H 22 CuO 14 , Cu (C 9 H 6 NO) 2 , C 14 H 8 CuF 2 O 8 S 2 , C 14 H 12 Cu
  • the carrier added to the mixed solution can form a promoter in the catalyst by using a group 15 or group 16 element incorporated therein.
  • a carrier mixed with a promoter may be prepared by mixing a powder of a material constituting the support and a solution in which a compound of a group 15 or 16 element is dissolved, followed by stirring and dehydration.
  • the pH of the catalyst for reducing nitrogen oxides can be adjusted to 5 or less by adding the acidic aqueous solution, and an active point corresponding to the following (1) can be prepared.
  • the pH of the catalyst for reducing nitrogen oxides greater than 5 it is possible to produce an active point corresponding to the following (2).
  • X is an integer having a value of 3 or 5.
  • the nitrogen oxide reduction system 100 includes an injection unit 120 and an exhaust unit 140 into which a chamber 110 in which a catalyst is accommodated and a reaction fluid 130 that is a flue gas containing nitrogen oxides are injected. ).
  • the catalyst is the catalyst for reducing nitrogen oxides 160 described above, and ammonia (NH 3 ) and nitrogen oxides (NO X ) as a reducing agent. ) In a molar ratio of 1: 1 may be injected to reduce the nitrogen oxides.
  • the chamber 110 may accommodate the catalyst 160 for reducing nitrogen oxides of the low temperature SCR reaction described above.
  • the catalyst may be contained in a fixed or extruded form to a structure such as honeycomb (honeycomb).
  • the reaction fluid 130 injected into the injection unit 120 may include ammonia and nitrogen oxide (NO X ), which are reducing agents of the low temperature SCR reaction, in a 1: 1 molar ratio.
  • NO X nitrogen oxide
  • the nitrogen oxide (NO X ) nitrogen monoxide (NO), nitrogen dioxide (NO 2 ) and the reducing agent ammonia (NH 3 ) proceeds in a molar ratio of 1: 1: 2. Since the reaction of Equation (7) is faster than other nitrogen oxide reduction reactions, in the nitrogen oxide reduction system 100, the reaction rate is controlled by controlling the composition ratio of the reaction fluid 130 injected into the injection unit 120. You can proceed. Accordingly, the reaction fluid 130 may include ammonia, which is a reducing agent of the low temperature SCR reaction, and nitrogen oxide (NO X ), which is a nitrogen oxide, in a 1: 1 molar ratio.
  • the reaction fluid 130 may further include water vapor (H 2 O) and sulfur dioxide (SO 2 ) in addition to nitrogen oxide (NO X ) as a reactant and ammonia (NH 3 ) as a reducing agent.
  • the nitrogen oxide reduction catalyst 160 includes copper vanadate having a large number of active sites, and poisoning of the catalyst surface by sulfur or sulfur dioxide (SO 2 ). Since it includes a promoter for improving resistance to, the reaction fluid 130 may further include other substances as impurities. This is because the flue gas, even with a same reaction fluid (130) without further purification, a high NOx conversion rate (NO X conversion) and high nitrogen selectivity (N 2 selectivity) in the actual use of the NOx reduction system 100 That means you can have
  • the catalyst 160 applied to the nitrogen oxide reduction system 100 of the present invention may have a diameter of 1 ⁇ m to 1,000 ⁇ m, and may load 0.1 g to 10 g into the chamber 110, and a copper copper vanadate. It includes crystal grains.
  • the reaction fluid 130 has a concentration of ammonia and nitrogen oxides, respectively, as a reducing agent of 100 ppm or more, and may be injected at a space velocity of 1,000 hr ⁇ 1 or more in a temperature range of 150 ° C. to 800 ° C.
  • the catalyst for reducing nitrogen oxides may be a Cu-rich copper vanadate crystal grain containing a large amount of copper (for example, Cu 3 V 2 O 8 or Cu 5 V 2 O 10 ) can be used as an active site to have high NO X conversion and N 2 selectivity.
  • copper for example, Cu 3 V 2 O 8 or Cu 5 V 2 O 10
  • Copper vanadate (nCuO-V 2 O 5 ) crystal grains of crystalline structure are prepared by the wet impregnation method. Specifically, 4.5 mmol of Cu (NO 3 ) 2 .3H 2 O is dissolved in 240 mL of distilled water to prepare an aqueous solution. Then, 3.0 mmol of NH 4 VO 3 is added, and 6 g of TiO 2 is added to the aqueous solution and stirred as a carrier. Thereafter, the solid obtained by evaporating distilled water is calcined (calcination) at 500 ° C. for 5 hours to prepare a Cu 3 catalyst (Cu 3 V 2 O 8 / TiO 2 ).
  • the Cu x catalyst refers to a catalyst prepared by dispersing copper vanadate crystal particles in Cu x V 2 O x +5 and being dispersed in a TiO 2 carrier.
  • Example 1 Cu 5 catalyst (Cu 5 V 2 O 10 / TiO 2 ) was prepared in the same manner except that 1.8 mmol of NH 4 VO 3 was added during preparation.
  • Example 1 a Cu 3 catalyst [Cu 3 V 2 O 8 / TiO 2- -Sb (1)] was manufactured in the same manner except that TiO 2 including Sb as a promoter was used as a carrier. do. Specifically, 49.5 g of TiO 2 was added to 500 mL of distilled water (containing 0.5 g of Sb) in which 1.23 g of Sb (CH 3 COO) 3 was dissolved, followed by stirring and dehydration for 5 hours at 500 ° C. by calcination (calcination) process to prepare a TiO 2 carrier of TiO 2 compared to 1% by weight of Sb it is incorporated.
  • Example 3 48.5 g of TiO 2 was added to 500 mL of distilled water (containing 1.5 g of Sb) in which 3.68 g of Sb (CH 3 COO) 3 was dissolved, thereby incorporating 3% by weight of Sb relative to TiO 2 .
  • a Cu 3 -Sb (3) catalyst [Cu 3 V 2 O 8 / TiO 2 -Sb (3)] was prepared in the same manner except that the prepared TiO 2 carrier was prepared.
  • Example 3 47.5 g of TiO 2 was added to 500 mL of distilled water (including 2.5 g of Sb) in which 6.14 g of Sb (CH 3 COO) 3 was dissolved, so that 5% by weight of Sb compared to TiO 2 was incorporated.
  • a Cu 3 -Sb (5) catalyst [Cu 3 V 2 O 8 / TiO 2 -Sb (5)] was prepared in the same manner except that the prepared TiO 2 carrier was prepared.
  • Example 1 Cu 1 catalyst (CuV 2 O 6 / TiO 2 ) was prepared by the same method except that 9.0 mmol of NH 4 VO 3 was added.
  • Example 1 Cu 2 catalyst (Cu 2 V 2 O 7 / TiO 2 ) was prepared by the same method except that 4.5 mmol of NH 4 VO 3 was added.
  • a catalyst (2V-5W / TiO 2 ) having a vanadium (V) content similar to that of the Cu 3 catalyst of Example 3 and including tungsten (W) was prepared. Specifically, 0.46 g of NH 4 VO 3 , 0.67 g of (NH 4 ) 10 (H 2 W 12 O 42 ) .4H 2 O and 0.84 g of C 2 H 2 O 4 .2H 2 O were mixed with 100 mL of distilled water. Is dissolved in and 9.3 g of TiO 2 is added, which is then stirred and dehydrated. Subsequently, calcination was performed at 500 ° C. for 5 hours to prepare a vanadium catalyst (2V-5W / TiO 2 ) including tungsten (W).
  • the catalysts for reducing nitrogen oxides of Comparative Example 1, Comparative Example 2, Example 1 and Example 2 were analyzed using an X-ray diffractometer (XRD), and the resulting X-rays
  • XRD pattern The diffraction pattern (XRD pattern) is shown in FIG. 4.
  • (A), (b), (c) and (d) of FIG. 4 mean X-ray diffraction patterns of Comparative Example 1, Comparative Example 2, Example 1 and Example 2, respectively.
  • all catalysts include a tetragonal anatase phase having a tetragonal crystal structure, meaning a TiO 2 carrier.
  • FIG. 5A shows the Cu 3 crystal grains of Example 1
  • FIG. 5B shows the Cu 5 crystal grains of Example 2.
  • FIG. 5 Referring to FIG. 5, in the case of Cu 3 , the (1 0 0) and (0 2 1) crystal planes of the monoclinic Cu 3 O 3 -V 2 O 5 have a monoclinic Cu 5 in the case of Cu 5. It can be seen that the (-1 1 1) and (-2 1 2) crystal faces of O 5 -V 2 O 5 appear.
  • the pore characteristics of the catalysts are physical adsorption of nitrogen gas (N 2) of Cu X catalysts with BET surface area values of 20 to 50 m 2 g -1 and BJH pore volume values of 0.1 to 0.3 cm 3 g -1 . physisorption).
  • Comparative Example 1 has the largest amount of H 2 -mediated reduction feature.
  • Comparative Example 1 while the main reduction reaction occurs in the temperature range of 350 °C or more, in the case of Examples 1 to 2 it was confirmed that the main reduction reaction occurs in the temperature range of 190-250 °C. This means that, for the low temperature SCR reaction, the catalysts of Examples 1 and 2 may have improved redox characteristics compared to those of Comparative Example 1.
  • Example 2 Example 3
  • Example 4 Example 5 Comparative Example 1 Comparative Example 2 mmol NH3 g -1 (via NH 3 -TPD) 4 2.4 4.1 3.8 3.9 1.6 3.6 ⁇ mol CO g -1 (via CO chemisorption) 1.1 2.0 0.6 2 1.1 ⁇ 0.1 ⁇ 0.1 mmol H2 g -1 (via H 2 -TPR) 2.6 2.0 1.9 3.4 3.4 2.9 2.5
  • the catalyst containing all copper vanadate was found to increase the amount of acid points present on the surface of the catalyst after sulfation.
  • the increased amount of acidic sites is mostly due to the increase in the number of Bronsted acid sites, which reduces the number of Lewis acid sites detectable with CO after sulfation of the catalyst surfaces. Inferred based on phenomena.
  • the H 2 -TPR analysis in Examples 1 and 2, it can be seen that the redox characteristics are improved after sulfation.
  • Examples 3 to 5 have almost the same number of acidic points as Example 1.
  • the CO-pulsed chemisorption analysis when the appropriate amount of Sb promoter is added, it can be seen that the density of Lewis acid site (Lewis acid site) is increased than in Example 1.
  • the redox characteristics of the catalysts of Examples 4 to 5 were also improved as compared to Example 1.
  • the Cu 5 catalyst of Example 2 has the best performance in an ideal environment in which water vapor (H 2 O) and sulfur dioxide (SO 2 ) do not exist. Can be expected.
  • the Cu 3 catalyst of Example 1 in the presence of water vapor (H 2 O) and sulfur dioxide (SO 2 ), the Cu 3 catalyst of Example 1, and for the catalysts to which the Sb promoter was added, the Cu 3 -Sb (3) of Example 4 It can be expected that the catalyst will have the best SCR catalyst performance.
  • the performance of the SCR process was measured using the catalysts of Comparative Example 1, Comparative Example 2, Example 1 and Example 2.
  • water vapor (H 2 O) and sulfur dioxide (SO 2 ) were measured without injecting, and conversion of nitrogen oxide [NO X conversion, shown in FIG. 6 (a)] and nitrogen selection was performed.
  • NO X conversion shown in FIG. 6 (a)
  • N 2 selectivity shown in Fig. 6 (b)] is shown in Fig. 6.
  • the reaction fluid contains 800 ppm NO X , 800 ppm NH 3 , 3 vol.% O 2 and the balance N 2
  • the total flow rate is 500 mL min -1 and the space velocity is 60,000 hr -1 .
  • Example 2 has superior performance compared to other catalysts. This is the result as described in the surface characteristic analysis of Experimental Example 1. That is, the catalysts of Examples 1 and 2 have a higher number of acidic points than those of Comparative Examples 1 and 2, and have better redox characteristics in a low temperature environment. In particular, since Example 2 is the highest with respect to the catalyst surface properties, it can be seen that the SCR system has the best reaction performance.
  • the performance of the SCR process was measured using the catalysts of Examples 1, 2 and Comparative Examples 1-2. In the temperature range of 150 °C to 400 °C, measured by injecting water vapor (H 2 O) and sulfur dioxide (SO 2 ), the conversion rate of nitrogen oxide [NO X conversion, shown in Figure 7 (a)] and nitrogen selectivity [N 2 selectivity, shown in Fig. 7 (b)] is shown in Fig. 7.
  • the reaction fluid is 800 ppm NO X , 800 ppm NH 3 , 3 vol.% O 2 , 6 vol.% H 2 O, 500 ppm SO 2 and the balance is N 2
  • Total flow rate is 500 mL min ⁇ 1
  • space velocity is 60,000 hr ⁇ 1 .
  • Example 1 has superior performance to other catalysts. This is the result as described in the surface characteristic analysis of Experimental Example 1.
  • the performance of the SCR process was measured using the catalysts of Comparative Example 3 and Examples 3 to 5.
  • the temperature range of 150 ° C to 400 ° C water vapor (H 2 O) and sulfur dioxide (SO 2 ) was injected and measured, and the conversion rate of nitrogen oxide [NO X conversion, shown in FIG. 8 (a)] and nitrogen selectivity [N 2 selectivity, shown in Fig. 8 (b)] is shown in Fig. 8.
  • the conditions of the SCR process are the same as in Experimental Example 3.
  • the catalyst of Examples 3 to 5 has better catalyst performance than the catalyst of Example 1. This is because, as described in Experimental Example 1, the surface characteristics of the catalyst were improved by the Sb oxide promoter, and the interaction between the catalyst surface and sulfur dioxide was reduced. In particular, according to Figure 8 it can be seen that the catalysts of Examples 4 and 5 are better than the commercial catalyst of Comparative Example 3.
  • the catalyst surfaces of Examples 1 and 4 were sulfated at 500 ° C. for 45 minutes, and the change of NO X conversion of nitrogen oxide was measured at 250 ° C., and the results are shown in FIG. 9.
  • the reaction fluid is 800 ppm NO X , 800 ppm NH 3 , 3 vol.% O 2 , 6 vol.% H 2 O, 500 ppm SO 2 and the balance N 2
  • the total flow rate is 500 mL min ⁇ 1
  • the space velocity is 60,000 hr ⁇ 1 .
  • the catalyst of Example 4 since the catalyst of Example 4 includes an Sb oxide promoter as in Experimental Example 4, it can be seen that the conversion of nitrogen oxide (NO X ) is smaller than that of Example 1. Specifically, for 100 minutes to 220 minutes after driving the SCR system, when only sulfur dioxide (SO 2 ) is injected, the catalyst of Example 4 does not have a decrease in nitrogen oxide (NO X ) conversion, but the catalyst of Example 1 decreases. I can see that. And, after 340 minutes, when both the steam (H 2 O) and sulfur dioxide (SO 2 ) is injected, it can be seen that the rate of reduction of the conversion of nitrogen oxide Example 4 is smaller. This is because the interaction between the catalyst surface and sulfur dioxide (SO 2 ) was reduced by the Sb promoter. Therefore, it can be seen that catalyst life is improved due to the catalyst of Example 4 further including an Sb promoter compared to the catalyst of Example 1.
  • the catalyst containing the copper copper vanadate salts of Examples 1 to 5 contained more acid sites than the catalysts of Comparative Examples 1 to 3, and the redox characteristics were decreased at low temperatures. You can see better. This means that the catalysts of Examples 1-5 may have better performance in low temperature SCR processes.
  • the number of acidic points of the catalyst increases, and the interaction with sulfur dioxide (SO 2 ) that interferes with the reduction reaction of nitrogen oxides is prevented. Can be reduced. Because of this, there is an effect of improving the performance and life of the catalyst.
  • the catalyst for reducing nitrogen oxides is a Cu-rich copper vanadate-based crystal grain (for example, Cu 3 V 2 O 8 or Cu containing a large amount of copper). 5 V 2 O 10 ) as the active point, it can have a high NO X conversion and N 2 selectivity.
  • Cu 3 V 2 O 8 / TiO 2 -Sb (3) prepared by Example 4 of 500 ppm SO 2 /3vol.% O 2 atmosphere and 500mL min -1 diluted with N 2 It is exposed for 60 minutes at 300 ° C. under a flow rate and then cooled to room temperature under an N 2 atmosphere.
  • the catalyst (S300) prepared through the SO Y 2 -functionalization by sulfation treatment under the above conditions is hereinafter referred to as Example 6.
  • Example 7 Except for modifying the temperature conditions applied in Example 6 to 400 °C, the functionalization using SO Y 2- on the surface of the Cu 3 V 2 O 8 / TiO 2 -Sb (3) catalyst under the same conditions as in Example 6 Conduct.
  • the catalyst (S400) prepared through this is hereinafter referred to as Example 7.
  • Example 8 Except for modifying the temperature conditions applied in Example 6 to 500 °C, the same conditions as in Example 6 to the functionalization by using SO Y 2- of the surface of the Cu 3 V 2 O 8 / TiO 2 -Sb (3) catalyst Conduct.
  • the catalyst (S500) prepared through this is referred to as Example 8 below.
  • a S400-Na catalyst was prepared in the same manner as in Comparative Example 4 except that S400 prepared according to Example 7 was used, which is referred to as Example 9.
  • Comparative Example 5 Preparation of deteriorated Cu 3 V 2 O 8 / TiO 2 -Sb (3) catalyst (pristine-thermal aging)
  • Example 4 Prepared by Example 4 Cu 3 V 2 O 8 / TiO 2 -Sb (3) with 3vol the catalyst to N 2 dilution (dilution). % O 2 / 6vol of.
  • a pristine-thermal aging catalyst was prepared by exposing to 200 hours at 550 ° C. for 200 hours under a water vapor atmosphere of 500 mL min ⁇ 1 and then cooling to room temperature under an N 2 atmosphere, which is referred to as Comparative Example 5.
  • Example 10 Except for using the S400 prepared by Example 7, to prepare a S400-thermal aging catalyst in the same manner as in Comparative Example 5, which is referred to as Example 10.
  • the catalysts for reducing nitrogen oxides of Examples 4 (pristine) and Examples 6 to 8 (S300 to S500) were analyzed using an X-ray diffractomer (XRD), and the results were derived.
  • XRD patterns The X-ray diffraction patterns (XRD patterns) are shown in FIG. 10.
  • all catalysts include crystal planes of an anatase phase (TiO 2 ) having a tetragonal crystal structure, meaning a TiO 2 carrier.
  • TiO 2 anatase phase
  • FIG. 10 it can be seen that in the catalyst of Example 4, crystal planes showing a crystal structure of monoclinic Cu 3 V 2 O 8 were observed.
  • Example 6 to 8 In, Cu 3 monoclinic crystal plane showing the crystal structure of V 2 O 8 that does not observed, which is, SO 2- Y by the sulfation process Cu 3 V This is because 2 O 8 was decomposed and combined with Cu or V to form new species. This can be confirmed by the orthorhombic CuSO 4 crystal faces observed in Examples 7 and 8.
  • FIG. 11 is a high resolution transmission electron microscopy (HRTEM) photograph of catalysts according to Comparative Examples and Examples of the present invention.
  • the catalysts of FIG. 11 have a porous structure comprising particles of species produced by the bonding of Cu 3 V 2 O 8 , Cu or V and SO Y 2- to an anatase agglomerate of several hundred nanometers in size.
  • HRTEM high resolution transmission electron microscopy
  • the pore properties of the catalysts have a BET surface area in the range of 30 m 2 g ⁇ 1 to 55 m 2 g ⁇ 1 , and the BJH pore volume is 0.18 cm 3 g ⁇ Have a value ranging from 1 to 0.23 cm 3 g ⁇ 1 .
  • Example 4 Example 6
  • Example 7 Example 8 mmol NH3 g -1 (via NH 3 -TPD) 3.1 7.5 7.0 3.8 ⁇ mol CO g -1 (via CO-pulsed chemisorption) 20.5 3.1 2.4 2.6 mmol H2 g -1 (via H 2 -TPR) 3.0 3.8 4.3 4.0
  • the catalysts (S300 to S500) of the sulfated Examples 6 to 8 were very different from the non-functionalized catalysts of Example 4. It can be seen that it contains a small amount of Lewis acid site. This is the result of coordinatively unsaturated, open active sites occupied by SO Y 2- species in the sulfate treatment of the catalyst.
  • the NH 3 -TPD (temperature-programmed desorption) experimental results shown in Table 4 indicate that the sulfated catalysts of Examples 6 to 8 were more plentiful than the non-functionalized catalysts of Example 4. It can be seen that it contains positive acid sites. This is the Y SO 2- functionalized catalyst via sulfation processes Y SO 4 2- -NH This is due to an increase in the number of Bronsted acid sites.
  • Example 6 and Example 7 contained a larger amount of acidic point than Example 8. This means that Examples 6 and 7, which can adsorb more ammonia in the NH 3 -SCR reaction, have superior reaction performance as compared with Examples 4 and 8.
  • H 2 -TPR temperature-programmed reduction
  • FIG. 12 is an XP spectra photograph of the O 1s region of the catalysts according to Comparative Examples and Examples of the present invention.
  • all of the catalysts are O 2 2- or oxygen species (O ⁇ ′) of H 2 O adsorbed on the surface of the catalyst, oxygen species (O ⁇ ) that are reactive and chemically adsorb, and lattice oxygen. It can be seen that it contains species (O ⁇ ).
  • the relative content of oxygen species (O ⁇ ) associated with the oxidation / reduction properties of the catalyst among the oxygen species was found to have the highest value in Example 7dl [ ⁇ 47mol. % (Example 7), ⁇ 35 mol. % (Examples 4, 6 and 8).
  • Example 7 which shows the best surface properties of Examples 4 and 6-8, has the best performance in the NH 3 -SCR reaction.
  • Example 4 In-situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy was used to characterize the SO bonds inherent in the SO Y 2- species combined with the metal species present on the surfaces of Examples 6-8. Is shown in FIG. 13.
  • Example 4 was pretreated for 1 hour at 400 ° C. under N 2 atmosphere, and then reference spectra at 300 ° C., 400 ° C., and 500 ° C. were obtained. Thereafter, Example 4 was at 300 °C, 400 °C, and 500 °C 30 minutes exposure under 1000ppm of O 2 atmosphere at a SO 2 /3vol.%, the time obtained after perspex column minus the reference spectrum at each temperature Shown. By this treatment, Example 4 was substantially changed to Examples 6, 7, and 8.
  • DRIFT In-situ diffuse reflectance infrared Fourier transform
  • FIG. 13 is a photograph showing DRIFT spectra under SO 2 / O 2 atmosphere and temperature of catalysts according to Comparative Examples and Examples of the present invention.
  • Example 6 In the case of Example 6 (300 °C), it can be seen that the peak of the SO bond having the characteristics of the covalent bond in the region of 1280 to 1450cm -1 , which is SO Y 2- is bonded to the single species of the metal species of the catalyst It has a form.
  • Example 8 500 °C
  • the peak of the SO bond having the characteristics of the ionic bond in the region of 1250cm -1 or less, which is SO Y 2- is a double bond form bonded to the metal species of the catalyst Means to have.
  • Example 7 (400 ° C.), it can be seen that SO Y 2-which is bonded to the metal species of the catalyst has a single bond form and a double bond form at the same time.
  • SO Y 2- which is bonded to the metal species of the catalyst has a single bond form and a double bond form at the same time.
  • Example 7 in which the various metal-SO Y 2- species are embedded, it can be predicted that only one metal-SO Y 2- species shows better NH 3 -SCR reaction performance compared to Examples 6 and 8, which are embedded. Can be.
  • 14 to 16 are graphs showing the NH 3 -SCR performance analysis results of various catalysts according to Comparative Examples and Examples of the present invention.
  • the performance of the SCR process was measured using the catalysts of Examples 4 and 6-8. In the temperature range of 150 ° C. to 400 ° C., it was measured without injecting sulfur dioxide (SO 2 ), and the conversion rate of nitrogen oxide [NO x conversion, shown in FIG. 14 (a)] and nitrogen selectivity [N 2 selectivity, FIG. 14 (b)] is shown in FIG.
  • the conditions of the NH 3 -SCR process the reaction fluid is 800ppm NO x , 800ppm NH 3 , 3vol. % O 2 , 6 vol. % H 2 O and N 2 , an inert gas, total flow rate is 500 mL min ⁇ 1 , and space velocity is 60,000 hr ⁇ 1 .
  • Example 7 has superior performance compared to other catalysts. This is the result as described in the surface characteristic analysis of Experimental Example 6. This is because the catalyst of Example 7 provides a higher amount of acidic activation points and more improved redox properties than Examples 4, 6 and 8.
  • the performance of the SCR process was measured using the catalysts of Comparative Example 4 (pristine-Na) and Example 9 (S400-Na). In the temperature range of 150 ° C. to 400 ° C., the measurement was performed without injecting sulfur dioxide (SO 2 ), and the conversion rate of nitrogen oxide [NO x conversion, shown in FIG. 15 (a)] and nitrogen selectivity [N 2 selectivity, FIG. 15 (b)] is shown in FIG. 15.
  • the reaction fluid is 800ppm NO x , 800ppm NH 3 , 3vol. % O 2 , 6 vol. % H 2 O and N 2 which is an inert gas
  • the total flow rate is 500 mL min ⁇ 1
  • the space velocity is 60,000 hr ⁇ 1 .
  • Example 9 (S400-Na) and Comparative Example 4 (pristine-Na) which intentionally poisoned the catalyst surface using an alkali metal species Na were used as Example 7 (S400) and It can be seen that NH 3 -SCR performance inferior to the catalyst of Example 4 (pristine). However, it can be seen that the catalyst of Example 9 shows better performance than the catalyst of Comparative Example 4. This means that Example 9, a sulfated catalyst, has improved resistance to alkali metals during NH 3 -SCR, compared to Comparative Example 4, a nonfunctionalized catalyst.
  • the performance of the SCR process was measured using the catalysts of Comparative Example 5 (pristine-thermal aging) and Example 10 (S400-themral aging). In the temperature range of 150 ° C. to 400 ° C., it was measured without injecting sulfur dioxide (SO 2 ), and the conversion rate of nitrogen oxide [NO x conversion, shown in FIG. 16 (a)] and nitrogen selectivity [N 2 selectivity, FIG. 16 (b)] is shown in FIG.
  • the reaction fluid is 800ppm NO x , 800ppm NH 3 , 3vol. % O 2 , 6 vol. % H 2 O and N 2 which is an inert gas
  • the total flow rate is 500 mL min ⁇ 1
  • the space velocity is 60,000 hr ⁇ 1 .
  • Example 10 the degraded catalysts of Example 10 (S400-themral aging) and Comparative Example 5 (pristine-thermal aging) were inferior to those of Example 7 (S400) and Example 4 (pristine), NH 3. It can be seen that SCR performance is shown. However, it can be seen that the catalyst of Example 10 shows better performance than the catalyst of Comparative Example 5. This means that Example 10, a sulfated catalyst, has improved resistance to degradation during NH 3 -SCR, compared to Comparative Example 5, a non-functionalized catalyst.
  • TiO 2 carrier (Sb / TiO 2) with a TiO 2 Sb than 3wt% incorporation.
  • an active point composed of copper and vanadium is prepared by a wet impregnation method.
  • a pH 5 catalyst was prepared in the same manner as in Example 11 except that the pH value was set to 5 by adding an aqueous HCl solution.
  • a pH 11 catalyst was prepared in the same manner as in Example 11 except that the pH value was set to 11 by adding an aqueous HCl solution.
  • the pH 1 catalyst prepared in Example 11 was exposed at 500 ° C. for 45 minutes at 500 ppm SO 2 / 3vol% O 2 atmosphere and 500 mL min ⁇ 1 flow rate diluted with N 2 , and then N 2 atmosphere Cool to room temperature under to prepare a pH 1 (S) catalyst.
  • a pH 5 (S) catalyst was prepared in the same manner as in Example 14, except that the pH 5 catalyst prepared in Example 12 was used.
  • a pH 11 (S) catalyst was prepared in the same manner as in Example 14 except that the pH 11 catalyst prepared in Example 13 was used.
  • the catalysts for reducing nitrogen oxides of Examples 11 to 16 were analyzed using an X-ray diffractomer (XRD), and the resulting X-ray diffraction patterns (XRD patterns) were also illustrated. 17 and FIG. 18.
  • XRD X-ray diffractomer
  • PH 1 shown in the figure means Example 11
  • pH 5 means Example 12
  • pH 11 means Example 13.
  • all catalysts include crystal planes of an anatase phase (TiO 2 ) having a tetragonal crystal structure, meaning a TiO 2 carrier.
  • TiO 2 anatase phase
  • two catalysts have crystal planes showing a crystal structure of monoclinic Cu 3 V 2 O 8 . This is because, when the pH value of the catalyst preparation solution is 5 or less, a favorable environment for forming a crystal structure of Cu 3 V 2 O 8 is created.
  • Example 13 of FIG. 17 it could be seen that crystal planes showing the crystal structures of orthorhombic V 2 O 5 and monoclinic CuO were observed. This is because, when the pH value of the catalyst preparation solution is 11, a favorable environment is formed for the formation of V 2 O 5 and CuO rather than the crystal structure of Cu 3 V 2 O 8 .
  • FIG. 18 is a graph showing an X-ray diffraction (XRD) pattern of catalysts according to Examples 14 to 16 of the present invention, and pH 1 (S) shown in FIG. PH 5 (S) means Example 15, pH 11 (S) means Example 16.
  • XRD X-ray diffraction
  • FIG. 19 is a high resolution transmission electron microscopy (HRTEM) photograph of catalysts according to Examples 11 to 13 of the present invention.
  • the catalyst of Figure 19 are a few hundred nanometers - to have a several tens of micrometers in size anatase TiO 2 loaf surface shape of a Cu oxide, V oxide, dispersed porous and Cu 3 V 2 O 8 with one or more active sites of the (anatase agglomerate) It was found.
  • the components of the catalysts prepared in Examples 11 to 16 were analyzed using X-ray fluorescence (XRF).
  • XRF X-ray fluorescence
  • the V content of the catalysts was almost the same at 1.9 ( ⁇ 0.1) wt%, and the molar ratio of Cu: V was also 1.6 ( ⁇ 0.1): 1, which is close to the theoretical molar ratio (1.5: 1).
  • XRF X-ray fluorescence
  • the S content of the catalysts prepared in Examples 14-16 is shown in Table 5. In the case of the S content of the catalysts, it shows a value of 20% or less of the total content of the metal species (Cu, V, Sb), which is the result of the analysis of the XRD pattern shown in FIG. Sulfation of the surface of the catalysts mainly results in functionalizing only the surface of the incorporated active site '.
  • Example S a (wt%) N NH3 b, e N CO c, e N H2 d, e Example 11 (pH 1) 0 1.0 One One Example 12 (pH 5) 0 1.4 2.4 1.6 Example 13 (pH 11) 0 1.0 0.8 2.0
  • Example 14 (pH 1 (S)) 0.7 1.5 0.7 1.7
  • Example 15 pH 5 (S)) 1.5 2.2 1.0 2.0
  • Example 16 (pH 11 (S)) 0.1 0.8 0.3 2.5
  • Example 13 prepared under basic conditions compared to those of Examples 11-12 (or Examples 14-15) prepared under conditions close to acidic / neutral. It can be seen that it contains a smaller amount of scattering points.
  • Example 13 (or Example 16) prepared under basic conditions is acidic. It was found that the redox characteristics were improved compared to those of Examples 11 to 12 (or Example 14 or Example 15) prepared under conditions close to neutral.
  • the catalysts of Examples 14 to 16 had peaks of SO bonds having covalent bond characteristics in the region of 1280 to 1450 cm -1 , which means that SO Y 2-which is bonded to the metal species of the catalyst was monodentally bonded. It has a form.
  • all catalysts have peaks of SO bonds having ionic bond characteristics in the region of 1250 cm ⁇ 1 or less. This means that SO Y 2- bonded with the metal species of the catalyst has a bidentate bond form.
  • the V O species on the surface in the region of 1850 to 2100cm -1 combines with SO Y 2- to show a peak.
  • the catalysts of Examples 14 and 16 were more preferably adsorbed with nitrogen oxide or ammonia than the catalyst of Example 15 to perform the NH 3 -SCR reaction. It means preferring to be combined (poisoned) with SO 2 rather than causing it.
  • the catalysts of Examples 14 to 16 are formed as a result of the sulfidation of the catalysts of Examples 11 to 13, wherein the catalysts of Examples 11 to 13 are used to prepare the catalysts of Examples 14 to 16 in the NH 3 -SCR experiment in the presence of SO 2 . It is sulfated under the same conditions as that used. Thus, in Example 12 (pH 5) prepared under conditions close to neutral, when the NH 3 -SCR reaction experiment in the presence of SO 2 proceeded, compared to Example 11 (pH 1) and Example 13 (pH 11) improved reaction Performance and resistance to SO 2 / AS / ABS.
  • 21 and 22 are graphs showing the results of NH 3 -SCR performance analysis at various reaction conditions of the catalysts according to the embodiments of the present invention.
  • the performance of the SCR process was measured using the catalysts of Examples 11-13.
  • H 2 O was injected but measured without injecting sulfur dioxide (SO 2 ), and the nitrogen oxide conversion rate [NO x conversion, shown in FIG. 21 (a)] and nitrogen selection were selected.
  • Fig. 21 shows the N 2 selectivity shown in Fig. 21B.
  • the reaction fluid contains 800ppm NO x , 800ppm NH 3 , 3vol% O 2 , 6vol% H 2 O and inert gas (N 2 ), the total The total flow rate is 500 mL min ⁇ 1 , and the space velocity is 60,000 hr ⁇ 1 .
  • Example 13 has superior performance to other catalysts. This is described in the surface characteristic analysis of Experimental Example 10
  • Example 13 provides the most improved redox properties, despite providing smaller amounts of acid points compared to Examples 11 and 12.
  • the experimental results shown in FIG. 21 indicate that pH 11 synthesized under basic conditions is more preferred as a catalyst for NH 3 -SCR units for automobiles compared to pH 1 and pH 5 catalysts synthesized under conditions near acid / neutral. it means.
  • the performance of the SCR process was measured using the catalysts of Examples 14-16.
  • sulfur dioxide (SO 2 ) was injected and measured, the conversion of nitrogen oxides [NO x conversion, shown in Figure 22 (a)] and nitrogen selectivity [N 2 selectivity, Figure 22 Shown in (b) of FIG. 22.
  • the catalysts of Examples 11-13 were sulphated under the same conditions as those applied for the preparation of NH 3 -SCR performance before Examples 14-16 catalysts to vary from the catalysts of Examples 14-16. It became.
  • the catalyst of Example 15 has superior performance to other catalysts. This is because, as mentioned in the surface property analysis of Experimental Example 10, the catalyst of Example 15 has improved durability against SO 2 in spite of the smaller number of acid points and inferior redox characteristics than the catalyst of Example 16. .
  • the experimental results shown in FIG. 22 show that the pH 5 catalyst synthesized at near neutral conditions is more preferred as a catalyst for NH 3 -SCR units for sinter plants / power plants / ships compared to the pH 1 and pH 11 catalysts synthesized at acidic or basic conditions. It means.
  • the present invention includes a cu-rich copper vanadate-based crystal grain containing a large amount of copper (for example, Cu 3 V 2 O 8 or Cu 5 V 2 O 10 ).
  • Industrial applications are very useful in that catalysts can be prepared to provide catalyst surfaces with high NO x conversion and high N 2 selectivity.
  • a promoter including copper vanadate-based crystal grains (Cu 3 V 2 O 8 or Cu 5 V 2 O 10 ) and oxides of group 15 or group 16 of the periodic table is dispersed in the carrier. Since the catalyst is prepared and the surface of the catalyst is sulfated to improve the performance of the catalyst for reducing nitrogen oxides, it can be said that the industrial use is very useful.
  • the present invention by the sulfate treatment of the surface of the catalyst to improve the active acid point (for example, Bronsted acid site) and oxidation / reduction characteristics (redox feature) to improve the NH 3 -SCR reaction performance, SO 2 / ABS, alkali metal species and it can be said that the industrial use is very useful because it can improve the durability of the catalyst against degradation.
  • active acid point for example, Bronsted acid site
  • oxidation / reduction characteristics redox feature

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Abstract

La présente invention concerne un catalyseur pour la réduction d'un oxyde d'azote et un système de réduction d'oxyde d'azote l'utilisant. La présente invention est caractérisée en ce qu'elle comprend : un promoteur comprenant un oxyde du Groupe 15 ou 16; des grains cristallins de vanadate de cuivre représentés par [formule chimique 1] ci-dessous; et un support supportant les grains cristallins de vanadate de cuivre et le promoteur. [Formule chimique 1] CuXV2OX+5, où X est un nombre entier ayant une valeur de 3 ou 5.
PCT/KR2019/000653 2018-02-07 2019-01-16 Catalyseur pour la réduction d'oxyde d'azote et son procédé de production WO2019156379A1 (fr)

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