WO2013187632A1 - 담체 공극 매몰형 ｓｃｒ 촉매 구조체 - Google Patents

담체 공극 매몰형 ｓｃｒ 촉매 구조체 Download PDF

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WO2013187632A1
WO2013187632A1 PCT/KR2013/005002 KR2013005002W WO2013187632A1 WO 2013187632 A1 WO2013187632 A1 WO 2013187632A1 KR 2013005002 W KR2013005002 W KR 2013005002W WO 2013187632 A1 WO2013187632 A1 WO 2013187632A1
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Prior art keywords
carrier
scr catalyst
catalytically active
catalyst
active material
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English (en)
French (fr)
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한현식
김은석
안능균
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Heesung Catalysts Corp
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Heesung Catalysts Corp
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Priority to EP13803774.2A priority Critical patent/EP2859944A4/en
Priority to CN201380035836.9A priority patent/CN104411403A/zh
Priority to JP2015517173A priority patent/JP2015519199A/ja
Publication of WO2013187632A1 publication Critical patent/WO2013187632A1/ko
Anticipated expiration legal-status Critical
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    • 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
    • B01J23/24—Chromium, molybdenum or tungsten
    • 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
    • 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
    • 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
    • B01D53/92—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
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional [3D] monoliths
    • 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
    • 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
    • F01N3/206—Adding periodically or continuously substances to exhaust gases for promoting purification, e.g. catalytic material in liquid form, NOx reducing agents
    • F01N3/2066—Selective catalytic reduction [SCR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20707—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20723—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20769—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20776—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • 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
    • 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
    • B01J35/34—Mechanical properties
    • B01J35/36—Mechanical strength
    • 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
    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
    • F01N2370/04—Zeolitic material
    • 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
    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
    • F01N2510/068—Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
    • 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
    • F01N3/24—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 constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2825—Ceramics
    • F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a carrier pore-embedded SCR catalyst structure, and more particularly, to an SCR catalyst which can be applied in high sulfur content exhaust gas treatment, a catalytically active material is deposited inside a carrier, and the catalyst inner wall is substantially catalytically active.
  • SCR selective catalytic reduction
  • SCR systems are used to reduce the emissions of nitrogen oxides from the exhaust of boilers, engines and furnaces.
  • ammonia is injected into the exhaust stream of the boiler with the catalyst.
  • Ammonia is converted into water and nitrogen by reducing a large amount of nitrogen oxides from the exhaust gas.
  • the denitrogen oxide catalyst used in the SCR system is expensive, it is desirable to be able to control the stoichiometry of the exhaust gas / ammonia / catalyst reaction.
  • Catalytically active substances such as denitrogen oxides are supported on a carrier of refractory inorganic material or metal material.
  • the catalyst used in the SCR system can be roughly divided into an extruded SCR catalyst and a coated SCR catalyst depending on the preparation method.
  • the extrusion type is a structure in which the active material and the carrier constituent material are prepared in the form of a slurry, and then extruded using an extruder, in which the structure is usually manufactured in a honeycomb structure in order to prevent the exhaust gas pressure drop due to the catalyst.
  • the coating type is a catalyst having an active material coated on a carrier in a honeycomb form of ceramic or metal material. More specifically, monolithic carriers in the form of fine parallel gas flow passages extending therefrom from the carrier inlet or outlet side of the honeycomb structure can be used, which passages are open so that fluid flows through them.
  • the passageway which is a substantially straight path from the fluid inlet to the fluid outlet, is then defined by the inner wall where the catalytically active material is coated as a washcoat so that the exhaust gas flowing through the passages contacts the catalytic material.
  • the flow path of the monolithic carrier may be of any suitable cross-sectional shape and size, such as trapezoidal, rectangular, square, sinusoidal, hexagonal, elliptical, circular, etc., and has a thin inner wall structure. Such structures may have from about 60 to about 900 or more gas inlet openings (ie, cells) per square inch of cross section.
  • Extruded SCR catalysts are usually applied to power plants and ships.
  • the vanadium pentoxide extrusion type catalyst is a fire-resistant supporting material such as titanium dioxide and denitrification active material as vanadium pentoxide as a main raw material.
  • a honeycomb extruded catalyst is used that is extruded after the binder additive is added.
  • catalysts used in high dust generation such as ships or power plants require considerable mechanical strength, but bunker C oil, which is a fuel for ship diesel engines or coal-fired power plants, contains more than 2% of sulfur. When exposed to sulfur for a long period of time there is a problem that the mechanical strength drops sharply.
  • the present invention is proposed to solve the problems of the conventional extruded or coated SCR catalyst applied in the treatment of high sulfur content exhaust gas, and relates to a pore-deposited or buried SCR catalyst structure, and more particularly to a catalytically active material.
  • the present invention relates to a deposited SCR catalyst structure which is deposited inside the support and substantially free of catalytically active material on the inner wall of the support.
  • the carrier has a honeycomb structure of 20% to 80% porosity, cordierite, silicon carbide, cordierite- ⁇ -alumina, silicon nitride , Zircon mullite, spodumene, alumina-silica-magnesia, zircony silicate, silicate, magnesium silicate, zircon, petalite, ⁇ -alumina, aluminosilicate, and the like, preferably made of cordierite.
  • the catalytically active material deposited inside the carrier is a vanadium series in which titanium oxide (TiO 2 ), tungsten oxide (WO 3 ), or molybdenum oxide (MoO 3 ) is added to vanadium, It may be a zeolite-based or base metal oxide, but is not limited thereto.
  • the deposited or buried SCR catalyst according to the present invention maintains almost the same compressive strength as new products even after exposure to high sulfur containing exhaust gas, thereby overcoming the mechanical weakness as in conventional extruded structures over time.
  • the deposition type SCR catalyst according to the present invention is such that the catalytically active material is deposited in the carrier pores, and thus the catalytically active material is retained even after prolonged exposure to the high sulfur-containing exhaust gas, thereby deviating from the inner wall of the carrier as in the conventional coating structure. The physical loss can be prevented, and the back pressure applied to the catalyst can be lowered because the carrier channel space is relatively wider than the conventional coated structure.
  • Figure 2 is a graph showing the results of the evaluation of the compressive strength effect by the sulfur component for the conventional extruded and coated SCR catalyst.
  • FIG 3 is a schematic cross-sectional view of a conventional coated SCR catalyst and a deposited SCR catalyst according to the present invention.
  • Figure 4 is a photograph of the catalytic active material distribution in the deposition type SCR catalyst according to the present invention.
  • FIG. 5 is a graph comparing the activity of the conventional SCR catalyst and the deposited SCR catalyst according to the present invention.
  • the buried type SCR catalyst structure according to the present invention relates to a deposited type SCR catalyst structure in which a catalytically active material is deposited inside a carrier and substantially no catalytically active material is present on the inner wall of the carrier.
  • deposit or “burying” means that the catalytically active material penetrates into the pores formed in the carrier and is supported in the pores, and the catalytically active material is not substantially coated on the inner wall of the carrier.
  • the porosity of the pore charge volume in the total volume of the carrier is preferably 20% to 80%. If the porosity is 20% or less, it is not possible to provide sufficient catalytic function for the SCR reaction, and if it is 80% or more, the mechanical strength is lowered, and thus, a carrier having a porosity of 40 to 70%, more preferably 65% is preferable. .
  • the carrier is preferably configured in a honeycomb form so that the pressure drop is minimized while the exhaust gas from the power plant or marine diesel engine passes through the catalyst.
  • Honeycomb or honeycomb-shaped structures are obvious to those skilled in the art, but outlined, have parallel gas flow passages extending at the carrier inlet front or outlet back, which passages open at the front and rear, and at the gas inlet front. It has open passageways, ie channels, which are substantially straight paths to the discharge backside, which are formed by thin inner walls.
  • the carrier according to the present invention is made of a ceramic material capable of providing the above-described high porosity, cordierite, silicon carbide, cordierite- ⁇ -alumina, silicon nitride, alumina-silica-magnesia, zircon silicate, silicate, It may be made of magnesium silicate, zircon, petalite, ⁇ -alumina, aluminosilicate and the like, and preferably made of cordierite.
  • the catalytically active material is deposited in a plurality of pores formed in the carrier.
  • the material deposited inside the carrier may be a vanadium-based, zeolite-based or base metal oxide in which titanium oxide (TiO 2 ), tungsten oxide (WO 3 ), or molybdenum oxide (MoO 3 ) is added to vanadium, but It is not limited.
  • the immersion or buried SCR catalyst production method is quantified so that the catalytically active material does not exist on the inner wall of the carrier so that substantially all catalytically active material is deposited inside the carrier and the catalytically active material does not exist on the inner wall surface. It is manufactured so as not to be different from the conventional method for producing a coated SCR catalyst. That is, the conventional coated SCR catalyst quantifies the catalytically active slurry so that a thick coating layer is formed on the inner wall of the carrier, but the deposited SCR catalyst according to the present invention substantially catalyzes the catalytically active slurry so that all catalytically active materials penetrate into the carrier pores.
  • the porous carrier is immersed in a slurry and then fired.
  • the deposited SCR catalyst of the present invention (a) measuring the porosity of the carrier, (b) determining the amount of catalytically active slurry that can be deposited entirely in the carrier pores, (c) catalytically active slurry to the carrier It can easily be prepared by the step of depositing, and (d) calcining the catalyst obtained from step (c).
  • the method for quantitative deposition in step (c) may be achieved by Korean Patent Application No. 10-2011-0098682 (catalytic support quantitative coating apparatus and method) filed on Sep. 29, 2011 by the present applicant, and the prior application. Is incorporated herein by reference.
  • the extruded catalyst used in this evaluation was a honeycomb extruded catalyst structure (diameter 1 inch, length 2 inch, 50) whose main material was TiO 2 and WO 3 as refractory support material and V 2 O 5 as the denitrification oxide active material. cpi).
  • the coating catalyst is a structure in which the refractory carrier is coated with the same catalytically active material (V 2 O 5 -TiO 2 -WO 3 ) on the inner wall of a cordierite honeycomb carrier (diameter 1 inch, length 2 inches, 50 cpi). to be.
  • FIG. 1 shows the results of the structural change when the extruded and coated catalysts were contacted with water after exposure to sulfuric acid gas (24 hours).
  • the catalyst structure gradually melts and almost collapses, whereas in the case of the coated catalyst, the carrier structure is maintained even when exposed to sulfuric acid gas, but the catalytically active material coated on the inner wall of the carrier is lost. It became.
  • the conventional extruded or coated catalyst is not suitable for the ship diesel engine and the power plant exhaust gas treatment containing a large amount of sulfur.
  • Figure 2 is a graph showing the results of the evaluation of the compressive strength effect by the sulfur component for the conventional extruded and coated SCR catalyst.
  • the compressive strength was Measured.
  • the extrusion type of the new product itself compared to the coating type, but the compressive strength is reduced significantly after the SO2 gas treatment or sulfuric acid gas treatment will ultimately collapse the catalyst structure.
  • coating type there is no change in strength even in SO 2 gas treatment or sulfuric acid gas treatment, but as shown in the results of FIG. The mold needed to improve its structure.
  • FIG. 3 is a schematic cross-sectional view of a coated SCR catalyst and a deposited SCR catalyst according to the present invention.
  • the carrier applied in the present invention is a highly porous carrier capable of depositing substantially all catalytically active ingredients. Accordingly, as illustrated in FIG. 3, in the deposition type catalyst, the washcoat (catalytically active ingredient) is all deposited inside the carrier, and thus the washcoat is substantially not present on the inner wall of the carrier.
  • the conventional coating catalyst uses a conventional refractory ceramic carrier so that the washcoat is applied to the inner wall of the carrier to a certain thickness. Therefore, the catalytically active component is deposited into the carrier pores to solve the problem of adhesion caused by the problem in the conventional coating catalyst. Furthermore, since the volume of exhaust gas flowing in the carrier channel is relatively increased compared to the coating catalyst, the back pressure is reduced, thereby improving the fuel efficiency of the engine.
  • Figure 4 is a photograph of the catalytic active material distribution in the deposition type SCR catalyst according to the present invention when applying a cordierite carrier having a 65% porosity. From the left picture to the right picture, 100 g / L, 135 g / L and 212 g / L were applied as dry gain (D / G). In other words, when 100 g / L or 135 g / L of catalytically active component is applied to a cordierite carrier having a 65% porosity, most of the catalytic components substantially penetrate into the carrier pores so that there is substantially no catalytic component contributing to the activity on the surface. .
  • the method for preparing a catalyst according to the present invention primarily comprises the steps of (a) measuring the porosity of the carrier, (b) determining the amount of catalytically active slurry that can be deposited entirely in the carrier pores, and (c) the catalytically active slurry as a carrier. By dipping in, and (d) calcining the catalyst obtained from step (c).
  • the catalytically active component is 3% V 2 O 5 / TiO 2
  • dry gain of 100g / L is deposited inside the carrier (300 cpsi) made of cordierite material having a porosity of 65%
  • the catalytically active component is 2.5% V 2 O 5 / TiO 2
  • the dry gain of 139.8 g / L is coated on the inner wall of the carrier (400 cpsi) made of cordierite material having a porosity of 35%.
  • the activity evaluation conditions of both catalysts were space velocity (SV): 50,000 1 / hr, feed gas component: 500 ppm NO, 500 ppm NH 3 , 10% O 2 , 5% H 2 O, N 2 balance.
  • SV space velocity
  • feed gas component 500 ppm NO, 500 ppm NH 3 , 10% O 2 , 5% H 2 O, N 2 balance.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Combustion & Propulsion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Toxicology (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

본 발명은 고황 함량 배기가스 처리에 있어서 적용되는 종래 압출형 또는 코팅형 SCR 촉매의 문제점을 해결하기 위하여 제안되는 것으로, 공극 침적형 또는 매몰형 SCR 촉매 구조체에 관한 것이고, 촉매활성물질이 담체 내부에 침적되고, 담체 내벽에는 실질적으로 촉매활성물질이 존재하지 않는 침적형 SCR 촉매 구조체에 관한 것이다.

Description

담체 공극 매몰형 ＳＣＲ 촉매 구조체
본 발명은 담체 공극 매몰형 SCR 촉매 구조체에 관한 것이고, 더욱 상세하게는 고황 함량 배기가스 처리에 있어서 적용될 수 있는 SCR 촉매에 있어서, 촉매활성물질이 담체 내부에 침적되고, 담체 내벽에는 실질적으로 촉매활성물질이 존재하지 않는 담체 공극 침적형 또는 매몰형 SCR 촉매 구조체에 관한 것이다.
일반적으로 산업, 다용도 보일러, 엔진 및 노(furnace)의 분야에서 시스템으로부터 방출되는 질소산화물 제어를 위한 선택적 촉매환원(SCR; selective catalytic reduction) 시스템이 활용되고 있다. SCR 시스템은 보일러, 엔진과 노의 배기가스로부터 질소산화물의 방출을 줄이는 데에 이용된다. 상기 시스템에서 암모니아는 촉매가 있는 보일러의 배기가스흐름에 분사된다. 암모니아는 배기가스로부터 다량의 질소산화물을 환원시켜 물과 질소로 전환하게 된다. SCR 시스템에 이용된 탈질소산화물 촉매는 고가이므로, 배기가스/암모니아/촉매반응의 화학양론을 제어할 수 있는 것이 바람직하다. 이러한 탈질소산화물과 같은 촉매활성물질은 내화 무기재료 또는 금속재질의 담체에 지지된다.
SCR 시스템에 사용되는 촉매는 제조방법에 따라 압출형 SCR 촉매 및 코팅형 SCR 촉매로 대분될 수 있다. 압출형이란, 활성물질 및 담체 구성 재료를 슬러리 형태로 제조한 후 압출기를 사용하여 압출 성형되는 구조이며, 이때 구조는 촉매로 인한 배기가스 압력강하를 방지하기 위하여 통상 벌집형 구조로 제작된다. 이와는 대조적으로 코팅형이란 세라믹 또는 금속 재질의 벌집형 형태의 담체에 활성물질이 코팅된 구조의 촉매이다. 더욱 상세하게로, 벌집형 구조의 담체 유입면 또는 배출면으로부터 이를 통해 연장되는 미세한 병렬 가스 유동 통로를 가지는 형태의 단일체 담체가 사용될 수 있으며, 상기 통로는 개방되어 있어 이를 통해 유체가 흐른다. 이때 유체 유입구로부터 유체 배출구까지 실질적으로 직선 경로인 통로는 촉매 활성물질이 워시코트(washcoat)로서 코팅되어 상기 통로를 통해 흐르는 배기가스가 촉매 물질에 접촉하도록 하는 내벽에 의해 한정된다. 단일체 담체의 유동 통로는 사다리꼴, 직사각형, 정사각형, 사인 곡선 형태, 육각형, 타원형, 원형 등 임의의 적합한 단면 형태 및 크기일 수 있고, 내벽이 얇은 채널 구조이다. 이러한 구조체는 단면의 평방인치 당 약 60 내지 약 900개 이상의 가스 유입 개구(즉, 셀)를 가질 수 있다.
발전소 및 선박에는 통상 압출형 SCR 촉매가 적용된다. 예를들면, 오산화이바나듐계 압출형 촉매는 내화성 담지재료로서 이산화티타늄, 탈질소 활성물질로는 오산화이바나듐이 주원료로 사용되며 원활한 압출을 위하여 유기물의 바인더 첨가제 및 성형 유지와 기계적 강도를 높이기 위하여 무기물의 바인더 첨가제가 첨가된 후 압출 성형되는 벌집형의 압출형 촉매가 사용된다. 그러나 선박 또는 발전소와 같은 다량의 분진이 발생하는 곳에서 사용되는 촉매는 상당한 기계적 강도가 요구되지만, 선박디젤엔진 또는 화력발전소 연료인 벙커C유에는 2%이상의 황이 함유되어 있어, 압출형 SCR 촉매가 장기간 황에 노출되는 경우 기계적 강도가 급격히 떨어지는 문제점이 있다. 또한, 촉매 구조가 붕괴하면서, SCR 촉매에 걸리는 배압이 증가되어 선박디젤엔진 연비가 열악해지는 등의 문제점이 있다. 한편, 코팅형 촉매를 적용하는 경우 코팅된 활성물질이 담체 내벽으로부터 이탈되는 등 촉매 활성 성분이 물리적으로 소실되는 문제점이 있다.
본 발명은 고황 함량 배기가스 처리에 있어서 적용되는 종래 압출형 또는 코팅형 SCR 촉매의 문제점을 해결하기 위하여 제안되는 것으로, 공극 침적형 또는 매몰형 SCR 촉매 구조체에 관한 것이고, 더욱 상세하게는 촉매활성물질이 담체 내부에 침적되고, 담체 내벽에는 실질적으로 촉매활성물질이 존재하지 않는 침적형 SCR 촉매 구조체에 관한 것이다.
비제한적으로, 본 발명에 의한 침적형 또는 매몰형 SCR 촉매구조체에 있어서, 담체는 벌집형 구조로 20% 내지 80% 다공성을 가지며, 코디어라이트, 탄화규소, 코디어라이트-α-알루미나, 질화규소, 지르콘 뮬라이트, 스포듀민, 알루미나-실리카-마그네시아, 규산 지르콘, 규선석, 규산 마그네슘, 지르콘, 페타라이트, α-알루미나, 알루미노실리케이트 등으로 이루어질 수 있으며, 바람직하게는 코디어라이트로 이루어진다. 본 발명에 의한 침적형 SCR 촉매구조체에 있어서, 담체 내부에 침적되는 촉매활성물질은 티타늄산화물(TiO2), 텅스텐산화물(WO3), 또는 몰리브덴산화물(MoO3)이 바나듐에 첨가된 바나듐계열, 제올라이트 계열 또는 비금속 (base metal)산화물일 수 있으나, 이에 한정되지 않는다.
본 발명에 의한 침적형 또는 매몰형 SCR 촉매는, 고황 함유 배기가스에 노출된 후에도 신품과 거의 동일한 압축강도를 유지하므로 시간 경과에 따른 종래 압출형 구조에서와 같은 기계적 취약성을 극복할 수 있다. 또한 본 발명에 따른 침적형 SCR 촉매는, 촉매활성물질이 담체 공극에 침적되어 있어 고황 함유 배기가스에 장기간 노출된 후에도 촉매활성물질이 유지되어 종래 코팅형 구조에서와 같이 담체 내벽에서 벗어지는 등의 물리적 손실을 방지할 수 있고, 종래 코팅형 구조체와 비교하여 상대적으로 넓은 담체 채널 공간이 유지되므로 촉매에 걸리는 배압이 낮아지는 효과가 있다.
도 1은 종래 압출형 및 코팅형 SCR 촉매에 대한 황 성분에 의한 형상 변경 평가 실험 사진이다.
도 2는 종래 압출형 및 코팅형 SCR 촉매에 대한 황 성분에 의한 압축강도 영향 평가 측정 결과 그래프이다.
도 3은 종래 코팅형 SCR 촉매 및 본 발명에 의한 침적형 SCR 촉매의 개략 단면도이다.
도 4는 본 발명에 의한 침적형 SCR 촉매에서의 촉매활성물질 분포 사진이다.
도 5는 종래 코팅형 SCR 촉매 및 본 발명에 의한 침적형 SCR 촉매 활성도 비교 그래프이다.
본 발명에 의한 매몰형 SCR 촉매 구조체는, 촉매활성물질이 담체 내부에 침적되고, 담체 내벽에는 실질적으로 촉매활성물질이 존재하지 않는 침적형 SCR 촉매 구조체에 관한 것이다.
본원에서 사용되는, ‘침적’또는 '매몰'이란, 담체에 형성되는 공극 내부로 촉매활성물질이 침투하여 공극내부에서 지지되는 것을 의미하며, 촉매활성물질은 담체 내벽에 실질적으로 코팅되어 있지 않다.
본 발명에서 촉매활성물질이 본 발명의 목적을 달성하도록 담체 내부에 침적되기 위하여, 담체 전 용적 중에서 공극 차지 용적의 비율인 다공도는 20% 내지 80%인 것이 바람직하다. 다공도가 20% 이하인 경우에는 SCR 반응에 충분한 정도의 촉매 기능을 제공할 수 없으며 80% 이상인 경우에는 기계적 강도가 저하되므로, 40 내지 70%, 더욱 바람직하게는 65%의 다공도를 가지는 담체가 바람직하다. 발전소 또는 선박디젤엔진에서 배출되는 배기가스가 촉매를 경유하면서 압력강하가 최소화되도록 담체는 바람직하게는 벌집형 형태로서 구성된다. 벌집형 또는 허니컴 형태의 구조는 본 분야의 당업자에게 명백하지만 개략적으로 기술하면, 담체 유입 전면 또는 배출 후면에서 연장되는 병렬 가스 유동 통로를 가지고, 상기 통로는 전면 및 후면에 개방되어, 가스 유입 전면에서 배출 후면까지 실질적으로 직선 경로인 개방 통로, 즉 채널을 가지고, 이들 채널은 얇은 내벽에 의해 형성된다.
본 발명에 의한 담체는 상기된 고도의 다공성을 제공할 수 있는 세라믹 재질로 이루어지며, 코디어라이트, 탄화규소, 코디어라이트-α-알루미나, 질화규소, 알루미나-실리카-마그네시아, 규산 지르콘, 규선석, 규산 마그네슘, 지르콘, 페타라이트, α-알루미나, 알루미노실리케이트 등으로 이루어질 수 있으며, 바람직하게는 코디어라이트로 이루어진다. 촉매활성물질은 담체에 다수 형성된 공극들에 침적된다. 담체 내부에 침적되는 물질은 티타늄산화물(TiO2), 텅스텐산화물(WO3), 또는 몰리브덴산화물(MoO3)이 바나듐에 첨가된 바나듐계열, 제올라이트 계열 또는 비금속 (base metal)산화물일 수 있으나, 이에 한정되지 않는다.
본 발명에 의한 침적형 또는 매몰형 SCR 촉매제조방법은, 담체 내벽에 촉매활성물질이 존재하지 않도록 정량화하여 실질적으로 모든 촉매활성물질이 담체 내부에 침적되고 내벽 표면에는 실질적으로 촉매활성물질이 존재하지 않도록 제조하는 것으로, 종래 코팅형 SCR 촉매제조방법과 다르지 않다. 즉, 종래 코팅형 SCR 촉매는 담체 내벽에 후박하게 코팅층이 형성되도록 촉매활성 슬러리를 정량하는 것이나, 본 발명에 의한 침적형 SCR 촉매는 실질적으로 모든 촉매활성물질이 담체 세공 내부로 침투하도록 촉매활성 슬러리를 정량한 후 다공성 담체를 슬러리에 침지한 후 소성하는 것이다. 즉 본 발명의 침적형 SCR 촉매는, (a) 담체의 다공도를 측정하는 단계, (b) 담체 공극에 전량 침적될 수 있는 촉매활성슬러리 함량을 결정하는 단계, (c) 촉매활성슬러리를 담체에 침적시키는 단계, 및 (d) 단계 (c)로부터 얻어진 촉매를 하소하는 단계에 의해 용이하게 제조할 수 있다. (c) 단계에서의 정량 침적방법은 본 출원인에 의해 2011-09-29 출원된 대한민국 특허출원번호 제10-2011-0098682호 (촉매지지체 정량 코팅장치 및 방법)에 의해 달성될 수 있으며, 상기 선출원은 참조로 본원에 포함된다.
이하 본 발명에 의한 침적형 촉매를 도면을 참조하여 설명한다. 먼저, 종래 압출형 촉매 및 코팅형 촉매의 문제점을 평가하고 본 발명을 상세히 설명한다.
도 1은 종래 압출형 및 코팅형 SCR 촉매에 대한 황 성분의 영향을 평가한 것으로 특히 황 성분에 의한 형상 붕괴 여부를 평가한 것이다. 본 평가에서 사용된 압출형 촉매는 내화성 담지물질로서 TiO2 및 WO3, 탈질소산화물 활성물질로는 V2O5이 주원료인 벌집구조의 압출형 촉매 구조체 (직경 1인치, 길이 2 인치, 50 cpi)이다. 또한 코팅형 촉매는 내화성 담체는 코디어라이트 재질의 벌집구조 담체 (직경 1인치, 길이 2 인치, 50 cpi) 내벽에 동일한 촉매활성물질 (V2O5-TiO2-WO3)이 코팅된 구조체이다. 도 1은 상기 압출형 및 코팅형 촉매들을 황산가스에 노출시킨 후 (24 시간) 물과 접촉시켰을 때의 구조 변경 결과를 나타낸 것이다. 도 1에서 볼 수 있듯이, 압출형 촉매의 경우 촉매 구조체는 서서히 녹아들어가 형태가 거의 붕괴된 반면, 코팅형 촉매의 경우 황산가스에 노출되어도 담체 구조는 유지되지만 담체 내벽에 코팅된 촉매활성재료는 소실되었다. 이러한 평가 결과, 종래 압출형 또는 코팅형 촉매는 황 성분이 다량 함유된 선박디젤엔진 및 발전소 배기가스 처리에 적합하지 않다는 것을 확인할 수 있었다.
도 2는 종래 압출형 및 코팅형 SCR 촉매에 대한 황 성분에 의한 압축강도 영향 평가 측정 결과 그래프이다. 압출형 및 코팅형 촉매를 상기된 바와 같이 황산가스로 처리하는 것 외에도, 1800 pm SO2, 10% H2O, 나머지 공기로 조성된 300℃의 SO2 가스에 24 시간 노출시킨 후, 압축강도를 측정하였다. 도 2에서 확인되는 바와 같이, 압출형은 코팅형과 대비하여 신품 자체가 압축강도가 떨어지지만 SO2 가스 처리 또는 황산가스 처리 이후에는 현저하게 압축강도가 낮아져 궁극적으로 촉매 구조체 붕괴가 될 것이다. 이에 반하여, 코팅형의 경우 SO2 가스 처리 또는 황산가스 처리에도 강도의 변화는 없지만, 도 1의 결과에서 밝힌 바와 같이 촉매활성성분들이 담체 내부로부터 이탈되는 부착 이상의 문제가 발생하므로, 압출형 및 코팅형은 구조 개량의 필요성이 대두되었다.
도 3은 코팅형 SCR 촉매 및 본 발명에 의한 침적형 SCR 촉매의 개략 단면도이다. 본 발명에서 적용되는 담체는 촉매활성성분을 실질적으로 모두 침적시킬 수 있는 고도의 다공성 담체이다. 따라서 도 3에 도시된 바와 같이 침적형 촉매는 워시코트 (촉매활성성분)이 담체 내부로 모두 침적되어 담체 내벽에는 워시코트가 실질적으로 존재하지 않는다. 이와 대비되어, 종래 코팅형 촉매는 통상의 내화 세라믹 재질의 담체를 사용하므로 워시코트는 담체 내벽에 일정 두께로 도포된다. 따라서 촉매활성성분이 담체 공극 내부로 침적되어 종래 코팅형 촉매에서 문제점으로 제기된 부착력의 문제를 해결할 수 있는 것이다. 더욱이, 담체 채널에는 배기가스가 유동할 수 있는 용적이 코팅형 촉매에 비하여 상대적으로 증가되므로 배압이 감소되고, 이에 따라 엔진의 연비 증진 효과를 기대할 수 있다.
도 4는 65% 다공도를 가지는 코디어라이트 재질의 담체를 적용할 때 본 발명에 의한 침적형 SCR 촉매에서의 촉매활성물질 분포 사진이다. 좌측 사진으로부터 우측 사진으로 갈수록, 촉매활성성분이 드라이 게인 (D/G)으로 100g/L, 135 g/L 및 212 g/L가 적용된 것이다. 즉 100g/L 또는 135 g/L의 촉매활성성분이 65% 다공도의 코디어라이트 담체에 인가되면 촉매성분들은 대부분 실질적으로 담체 공극으로 침투되어 표면에는 활성에 기여하는 촉매성분은 실질적으로 존재하지 않는다. 그러나 212 g/L의 활성성분이 적용되는 경우에는 공극을 충전하고도 남은 활성성분이 담체 내벽에 도포되어 코팅형-유사한 구조체를 이룬다. 본 발명에 의한 침적형 촉매는 상기 코팅형-유사한 구조체를 이루기 직전의 함량의 촉매활성성분을 가지며, 이러한 촉매성분은 실질적으로 세공 내부로 모두 침투되어 하소되어 공극 내부에 지지된다. 따라서 본 발명에 의한 촉매제조방법은 일차적으로 (a) 담체의 다공도를 측정하는 단계, (b) 담체 공극에 전량 침적될 수 있는 촉매활성슬러리 함량을 결정하는 단계, (c) 촉매활성슬러리를 담체에 침적시키는 단계, 및 (d) 단계 (c)로부터 얻어진 촉매를 하소하는 단계에 의해 제조할 수 있다.
도 5는 종래 코팅형 SCR 촉매 및 본 발명에 의한 침적형 SCR 촉매 활성도 비교 그래프이다. 침적형 촉매에서 촉매활성성분은 3% V2O5/TiO2, 드라이 게인 100g/L의 함량이, 다공도 65%의 코디어라이트 재질의 담체 (300cpsi) 내부에 침적된 것이며, 코팅형 촉매에서 촉매활성성분은 2.5 % V2O5/TiO2, 드라이 게인 139.8 g/L의 함량이, 다공도 35%의 코디어라이트 재질의 담체 (400cpsi) 내벽에 코팅된 것이다. 이들 양 촉매의 활성평가 조건은 공간속도 (SV) : 50,000 1/hr, 공급가스성분: 500 ppm NO, 500 ppm NH3, 10% O2, 5% H2O, N2 balance이었다. 도 5에 확인되는 바와 같이, 침적형 또는 매몰형 SCR 촉매는 코팅형 SCR 촉매 대비하여 거의 동일한 촉매활성을 보였다.

Claims (5)

  1. 담체 및 촉매활성물질로 구성되는 고황 함유 배기가스의 질소산화물 처리용 촉매구조체에 있어서, 촉매활성물질이 담체 내부 공극에만 침적되고, 담체 내벽에는 실질적으로 촉매활성물질이 존재하지 않도록 구성되는, 담체 공극 매몰형 SCR 촉매 구조체.
  2. 제1항에 있어서, 상기 담체의 다공도는 20% 내지 80%의 범위인 것을 특징으로 하는, 담체 공극 매몰형 SCR 촉매 구조체.
  3. 제1항에 있어서, 상기 담체는 벌집형 구조인 것을 특징으로 하는, 담체 공극 매몰형 SCR 촉매 구조체.
  4. 제1항 내지 제3항 중 어느 하나의 항에 있어서, 상기 담체는 코디어라이트, 탄화규소, 코디어라이트-α-알루미나, 질화규소, 지르콘 뮬라이트, 스포듀민, 알루미나-실리카-마그네시아, 규산 지르콘, 규선석, 규산 마그네슘, 지르콘, 페타라이트, α-알루미나, 및 알루미노실리케이트로 이루어진 세라믹 재질에서 선택되는 것을 특징으로 하는, 담체 공극 매몰형 SCR 촉매 구조체.
  5. 제1항에 있어서, 상기 촉매활성물질은 티타늄산화물(TiO2), 텅스텐산화물(WO3), 또는 몰리브덴산화물(MoO3)이 바나듐에 첨가된 바나듐계열, 제올라이트 계열 및 비금속 (base metal)산화물로 이루어진 군에서 선택되는 것을 특징으로 하는, 담체 공극 매몰형 SCR 촉매 구조체.
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JP2021000631A (ja) * 2014-07-31 2021-01-07 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ 触媒を製造するための方法及び触媒物品
CN111036192A (zh) * 2019-12-23 2020-04-21 中国科学院过程工程研究所 一种涂覆型耐磨钒系脱硝催化剂及其制备方法与应用
CN111036192B (zh) * 2019-12-23 2021-08-06 中国科学院过程工程研究所 一种涂覆型耐磨钒系脱硝催化剂及其制备方法与应用

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KR101336597B1 (ko) 2013-12-16
EP2859944A1 (en) 2015-04-15

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